Microporous Poly(tri(4-ethynylphenyl)amine) Networks: Synthesis, Properties, and Atomistic Simulation

Abstract

Microporous poly(tri(4-ethynylphenyl)amine) networks were synthesized by palladium-catalyzed Sonogashira-Hagihara cross-coupling chemistry with apparent Brunauer-Emmet-Teller (BET) specific surface areas in the range 500-1100 m2/g. It was found that very fine synthetic control over physical properties such as BET surface area, Langmuir surface area, micropore surface area, micropore volume, and bulk density could be achieved by varying the average monomer strut length. The micropore structure and micropore surface area were rationalized by atomistic simulations for one network, NCMP-0, based on multiple physical characterization data

Polymers of Intrinsic Microporosity

“…These materials include the much studied crystalline metal organic frameworks (MOFs) [2][3][4][5] and purely organic but structurally similar covalent organic frameworks (COFs) [6][7][8]. In addition, there has been intense activity in the synthesis and study of amorphous polymer networks with a wide variety of structures such as the hyperCrosslinked polymers (HCPs) [9][10][11][12] and microporous conjugated polymers (MCPs) [13][14][15][16][17][18]. The rapid recent progress in the synthesis of microporous network polymers has been reviewed extensively [19,20].…”

One-step synthesis of conjugated enynenitriles from bromocyanoacetylene

“…(E)-3-(diisopropylamino)-5-(p-tolyl)pent-2-en-4-ynenitrile (14). The general procedure was followed with 4-ethynyltoluene and diispropylamine.…”

“…However, enynes 20, 21 and 22 were obtained from the corresponding ynamide 13 , para-methoxyphenylacetylene and ethynylferrocene in 23, 66 and 80% yields respectively. Interestingly, when using a reactant bearing two terminal acetylenes separated by a biphenyl unit, 14 only one CC triple bond reacted to afford compound 23 in 44% yield. This observation opens possibilities to further functionalize this kind of compounds.…”

Post-synthesis modification of porous organic polymers with amine: a task-specific microenvironment for CO2 capture

“…Various categories of novel materials with extraordinary porosity have been discovered, including silicas (Suhendi et al 2013), zeolites (Wakihara et al 2010), metal-organic frameworks , zeolitic imidazolate frameworks (Cai et al 2014) and carbon materials (Sevilla and Fuertes 2011). With the advantages of outstanding BET surface area and stability, tremendous porous organic polymers (POPs) have been designed (Jiang et al 2009;Dawson et al 2012;Zhao et al 2012;Han et al 2013;Liu et al 2013;Zhu et al 2013;Thompson et al 2014;Zhu and Zhang 2014;Puthiaraj et al 2015). More importantly, the organic skeletons of POPs give rise to their easy-to-functionalize nature so that enhancement of CO 2 /N 2 selectivity is able to be realized via the incorporation of CO 2 -philic groups into networks (Thomas 2010).…”