Fluorinated Polymers via Para-Fluoro-Thiol and Thiol-Bromo Click Step Growth Polymerization

Click reactions are utilized widely to modify chain ends and side groups of polymers while click polymerizations based on step-growth polymerization of bifunctional monomers have recently attracted increased attention of polymer chemists. Herein, the combination of two highly efficient click reactions, namely para-fluoro-thiol click and thiol-bromo substitution reactions, is demonstrated to form fluorinated polymers with tuned hydrophobicity owing to the nature of the dithiol linker compound. The key compound in this study is 2,3,4,5,6-pentafluoro benzyl bromide that provides the combination of thiol click reactions. The thiols used here are 4,4-thiobisbenzenthiol, 2,2'-(ethylenedioxy) diethanethiol, and 1,2-ethanedithiol that allow tuning of the properties of obtained polymers. The step-growth click reaction conditions are optimized by screening the effect of reaction temperature, base, solvent, and stochiometric ratio of the compounds. Thermal properties and hydrophobicity of synthesized polymers are determined via water contact angle, thermogravimetric analysis and differential scanning calorimetry measurements, showing thermal stability up to 300 °C, glass transition temperatures ranging from -25 to 82 °C and water contact angles ranging from 55 to 90 °C.