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

Abstract

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.

Graphical Abstract

Keywords:

• Polythioether
• organocatalyst
• thiol-Michael
• thiol-para-fluoro click
• post-polymerization modification

Disclosure statement

No potential conflict of interest was reported by the authors.

Additional information

Funding

This work was supported by the Research Fund of the Istanbul Technical University (Project Number: TAB-2021-42822).