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A new open-chain ether-linked polymer has been prepared via nucleophilic aromatic substitution reaction on a C-F bond of 1,4-dibromo-2,5-difluorobenzene by using 2,2-bis(4-hydroxyphenyl) hexafluoropropane (bisphenol AF or BAF). The new polymer (PE-AF) has shown a good solubility in non-polar solvents, good thermal stability (up to 300 °C) and random surface morphology. Tailoring these properties has been achieved by utilizing the post-modification synthetic methodology on the bromo-sites of the polymer backbone via the application of an Ullmann coupling reaction with aniline to form the polymer (PE-Sec-NHPh). The successful synthesis of the polymers has been confirmed by elemental analysis, infrared spectroscopy (IR), 1H- and 13C-NMR and 13C CP-MAS solid state. Upon incorporation of the aniline linker, the nitrogen content increased when compared with the parent polymer chain, and thus PE-Sec-NHPh revealed a higher thermal stability up to 350 °C and a more uniformly aggregated morphology (spherical particles ca. 0.3–0.1 µm). A further evaluation has been conducted on the polymers by measuring their surface tendency toward carbon dioxide capture. Interestingly, despite their non-porous nature, the polymers demonstrated a reasonable amount of gas capture that reached 90.0 and 41.0 mg/g for PE-Sec-NHPh and PE-AF, respectively. Furthermore, the calculated CO2 binding affinities of the polymers are consistent with data reported previously in the literature.

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Post-Functionalization of Bromo-Substituted Ether-Linked Polymers via Ullman Coupling Reaction: Synthesis, Characterization and Their Role toward Carbon Dioxide Capture