New Hyper-Crosslinked Partly Conjugated Networks with Tunable Composition by Spontaneous Polymerization of Ethynylpyridines with Bis(bromomethyl)arenes: Synthesis, Spectral Properties, and Activity in CO2 Capture

• Published in: Macromolecular chemistry and physics Vol. 214; no. 24; pp. 2856 - 2866
• Main Authors: Petrášová, Sabina, Zukal, Arnošt, Brus, Jiří, Balcar, Hynek, Pastva, Jakub, Zedník, Jiří, Sedláček, Jan
• Format: Journal Article
• Language: English
• Published: Weinheim Blackwell Publishing Ltd 01.12.2013; Wiley
• Subjects: Applied sciences; CO2 capture; conjugated polymers; ethynylpyridine; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; polyacetylenes; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; spontaneous polymerization; One pot reaction; Molecular structure; Carbon dioxide; Adsorption isotherm; Photoluminescence; Adsorption capacity; Bromocarbon; Luminescent material; ethynylpyridine; Optical properties; Crosslinked polymer; spontaneous polymerization; conjugated polymers; Autopolymerization; Bromine containing polymer; Crosslinking; capture; Experimental study; CO; Organic adsorbent; Gas solid adsorption; polyacetylenes; Preparation; Acetylene derivative polymer; Unsaturated polymer
• ISSN: 1022-1352; 1521-3935
• DOI: 10.1002/macp.201300540

Spontaneous catalyst‐free polymerizations of 4‐ethynylpyridine (4EPy) and 2‐ethynylpyridine with bifunctional quaternizing agents (QAs) of bis(bromomethyl)arenes provide highly crosslinked polymer networks in high yields. 13C cross‐polarization magic‐angle spinning (CP/MAS) NMR, Fourier transform IR (FTIR) and diffuse reflectance vis spectroscopy confirm that these networks consist of polyacetylene main chains substituted with pyridyl and pyridiniumyl groups, the latter interconnected with –CH2(arylene)CH2– linkers. Variation of the 4EPy/QA ratio in the polymerization feed results in networks with different extents of crosslinking and pyridyl/pyridin­iumyl ratio (N/N+ from 0 to 1.32). Networks exhibit photolumi­nescence and are also moderately active in CO2 capture (the highest uptake is 16.4 cm3 (STP) g−1 at 293 K and an equilibrium CO2 pressure of 750 Torr). Polymerizations of 4‐, and 2‐ethynylpyridine with bifunctional quaternizing agents of bis(bromomethyl)arenes provide highly crosslinked networks with polyacetylene main chains substituted by pyridyl and pyridiniumyl groups and crosslinked via ‐CH2(arylene)CH2‐ linkers. Depending on the synthesis conditions, the networks differ in crosslinking extent and pyridyl/pyridiniumyl ratio. The networks exhibit photoluminescence and CO2 capture.