Experimental and Computational Approaches to Sulfonated Poly(arylene ether sulfone) Synthesis Using Different Halogen Atoms at the Reactive Site

HIGHLIGHTS: The effect of differences in the halogen atoms at the ends of the biphenyl sulfone monomers on polymerization spontaneity was investigated through computer simulations and experiments. The polymerization process of SPAES was predicted using the first-principle calculation method. The simulation feasibility of polymer synthesis was verified experimentally. This approach based on quantum mechanics can even be effective in underlying polymer synthesis. ABSTRACT: Engineering thermoplastics, such as poly(arylene ether sulfone), are more often synthesized using F-containing monomers rather than Cl-containing monomers because the F atom is considered more electronegative than Cl, leading to a better condensation polymerization reaction. In this study, the reaction’s spontaneity improved when Cl atoms were used compared to the case using F atoms. Specifically, sulfonated poly(arylene ether sulfone) was synthesized by reacting 4,4′-dihydroxybiphenyl with two types of biphenyl sulfone monomers containing Cl and F atoms. No significant difference was observed in the structural, elemental, and chemical properties of the two copolymers based on nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray diffraction, transmission electron microscopy, and electrochemical impedance spectroscopy. However, the solution viscosity and mechanical strength of the copolymer synthesized with the Cl-terminal monomers were slightly higher than those of the copolymer synthesized with the F-terminal monomers due to higher reaction spontaneity. The first-principle study was employed to elucidate the underlying mechanisms of these reactions.