Polymer of Intrinsic Microporosity Incorporating Thioamide Functionality: Preparation and Gas Transport Properties

Abstract

Gas separation membranes are of interest for a variety of important applications, such as air separation, hydrogen recovery, carbon dioxide capture and the recovery of volatile organics from gas streams. 1 Membrane processes offer energy-efficient and lowcost solutions for many industrial problems. High free volume

Polymers of Intrinsic Microporosity

“…These include simple hydrolysis groups to provide carboxylic acids [69,70], reaction with P 2 S 5 to provide thioamines [71], reaction of hydroxylamine to give amidoximes [72], and the reaction of sodium nitride to provide tetrazole functionality (Scheme 2) [73].…”

“…For some rigid substituents, such as fused fluorenes (e.g., A8), some modest enhancement has been noted [76] but in most cases it appears that the substituents fill the microporosity generated by the packing of the polymer chains. Modifications to the nitrile substituents of PIM-1 to introduce carboxylic acid, thioamide, and tetrazole groups all significantly reduce the apparent surface area presumably due to the hydrogen bonding properties of these groups increasing polymer cohesion and improving packing [69,71,73]. However, the introduction of amidoxime substituents does not reduce significantly the apparent surface area and has thus been termed a "non-invasive" modification [72].…”

Photo-oxidative enhancement of polymeric molecular sieve membranes

“…Currently, there are several strategies to improve the separation performance of PIMs membranes: (i) enhancing the rigidity of polymer chain by synthesis of new monomers 12,[27][28][29][30] , (ii) postsynthetic modification of PIMs polymer 10,25,31 , (iii) mixed matrix membranes [32][33][34] and (iv) crosslinking induced by chemical 35 or heat treatment 36 . Ultraviolet light irradiation is a widely used technique for processing of polymer materials 8,[37][38][39][40] , for example, polymerization of novel gas-separation membranes 40 , creating nanostructures from block copolymer 8 , or surface modification of polymeric films (for example, polyimides and polydimethylsiloxane) 8,[37][38][39] .…”

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

“…In recent years, novel building blocks have been intensively investigated for the construction of three-dimensional microporous organic polymers, and the post-modification of microporous organic polymers also has been widely applied to synthesize novel microporous materials [9][10]. In previous publication [3], we reported the preparation of the triptycene-based micorporous polymer functionalized with CO 2 -philic tetrazole moieties via ZnCl 2 -catalyzed post-polymerization for CO 2 -capture application.…”

“…The fused-ring skeleton and threefold symmetry shape results in "internal molecular free volume," where the 3D spatial orientation reduces intermolecular contact between the extended planar struts of the rigid framework, thus reduces the packing within the solid [11]. In addition, the terephthalonitrile unit is rich in nitrile groups, which are the potential reaction sites for constructing diversified materials by post-modification, such as the carboxylated polymer and the polymer pending with tetrazole moieties [10]. In this study, the thioamide functionality by postpolymerization via the thionation of the aromatic nitriles are introduced to enhance the the polymer and gas species interactivity.…”