Amination of ether-linked polymers via the application of Ullmann-coupling reaction: synthesis, characterization, porosity, and thermal stability evaluation

Abstract

In this report, an open-chain ether-linked polymer (PE-AF) has been prepared via one-step co-condensation polymerization of 1,4-dibromo-2,5-difluorobenzene with bisphenol AF. The new polymer has shown a good solubility in non-polar solvents, good thermal stability (up to 300 °C), high char residue with a limiting oxygen index (LOI) of 33.5, surface morphology with random fluffy-like texture, and a non-porosity nature with a surface area (SA) of 35 m²g⁻¹. Tailoring these properties has been achieved by considering post-modification on the Bromo-sites of the polymer backbone. The post-modification was attained by applying Ullmann-coupling reaction of the Bromo-sites of PE-AF and aromatic diamines in presence of a catalytic amount of copper iodide. Upon inclusion of the aromatic diamines within the polymer’s backbone, the new polymers have depicted aggregated surface morphology (e.g. spherical particles ca. 0.3–0.1 µm), pronounced porosity nature (SA up to 354 m²g⁻¹), varied range of pore size distribution, and higher thermal stability with lower char residue contents when compared with PE-AF. The successful production of the polymers was confirmed by (C, H, O, and N) elemental analysis, solid-state ¹³C-NMR, and infrared (IR) spectroscopy. The application of Ullmann-coupling raises the opportunity to create cavities and pores within the polymer’s framework. Though this modification lowered the LOI of the polymers and their flame-retardant tendency, it enhanced their opportunity for gas capture and separation applications.

Keywords:

• Ether-linked polymers
• porous polymers
• Ullmann-coupling reaction
• thermal stability

Acknowledgments

The authors gratefully acknowledge the water, environment, and arid regions research center at Al al-bayt University-Jordan for the polymers characterizations and Tafila Technical University (grant # 122/2020).