A Straightforward Method for Fluorinated Polythioether Synthesis

The synthesis of fluorinated polymers via efficient routes along with mild experimental conditions is always desirable in terms of synthetic polymer chemistry. In this work, a straightforward method for fluorinated polythioether synthesis was developed. A commercially available electron-deficient alkyne compound, namely 4,4,4-trifluoro-2-butynoate (1), linked to both trifluoromethyl (CF₃) and ester units was polymerized with various dithiols by using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as a catalyst at room temperature, yielding CF₃-substituted polythioethers (CF₃-polythioethers). Unlike common polymerization methods (anionic and radical) described in the literature, which include harsh conditions to produce CF₃-substituted polymers, the synthetic methodology followed in this study offers mild conditions, and CF₃-polythioethers with high molecular weights (M_w, up to 21.1 kDa in 1 min and up to 42.5 kDa in 1 h) were obtained in high yields in reasonably short durations. The judicious combination of polythioether chemistry with a rapid polymerization method was introduced in this study to open a way for the development of novel fluorinated polymeric materials.