Post-polymerization modification of pentafluorophenyl-functionalized polythioether via thiol-para-fluoro click reaction

In this work, a rapid polymerization method was combined with thiol-para-fluoro (TPF) “click” post-polymerization modification (PPM) strategy. To this end, a reactive monomer, namely bis((perfluorophenyl)methyl) but-2-ynedioate, was specifically designed and used in the synthesis of polythioether via thiol-Michael addition reaction by using 1,6-hexanedithiol (HDT) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as a catalyst, and the reaction proceeded at room temperature for 5 min to give the pristine polythioether P0. This polymer was then used as a platform to perform PPM with various thiol compounds. The PPM reactions showed quantitative efficiency in 4 h with moderate to high yields. All modified polymers were analyzed with ¹H, ¹³C, and ¹⁹F NMR analyses, and molecular weights were calculated by using GPC. It is believed that combining such polymerization and PPM reactions can be a very useful tool to obtain polymers having different structures for different purposes. Hence, this work introduces a new type of polymer backbone that can be rapidly prepared and undergo a relatively fast PPM.