SuFEx-Based Polysulfonate Formation from Ethenesulfonyl Fluoride-Amine Adducts

Angew Chem Int Ed Engl. 2017 Sep 4;56(37):11203-11208. doi: 10.1002/anie.201701160. Epub 2017 May 18.

Abstract

The SuFEx-based polycondensation between bisalkylsulfonyl fluorides (AA monomers) and bisphenol bis(t-butyldimethylsilyl) ethers (BB monomers) using [Ph3 P=N-PPh3 ]+ [HF2 ]- as the catalyst is described. The AA monomers were prepared via the highly reliable Michael addition of ethenesulfonyl fluoride and amines/anilines while the BB monomers were obtained from silylation of bisphenols by t-butyldimethylsilyl chloride. With these reactions, a remarkable diversity of monomeric building blocks was achieved by exploiting readily available amines, anilines, and bisphenols as starting materials. The SuFEx-based polysulfonate formation reaction exhibited excellent efficiency and functional group tolerance, producing polysulfonates with a variety of side chain functionalities in >99 % conversion within 10 min to 1 h. When bearing an orthogonal group on the side chain, the polysulfonates can be further functionalized via click-chemistry-based post-polymerization modification.

Keywords: SuFEx reaction; bifluoride salt; click chemistry; ethenesulfonyl fluoride; polysulfonate formation.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Amines / chemistry*
  • Aniline Compounds / chemistry
  • Benzhydryl Compounds / chemistry
  • Click Chemistry
  • Ethylenes / chemistry*
  • Fluorides / chemistry*
  • Organosilicon Compounds / chemistry
  • Phenols / chemistry
  • Polymerization
  • Sulfonic Acids / chemistry*

Substances

  • Amines
  • Aniline Compounds
  • Benzhydryl Compounds
  • Ethylenes
  • Organosilicon Compounds
  • Phenols
  • Sulfonic Acids
  • t-butyldimethylsilyl compounds
  • ethylene
  • bisphenol A
  • Fluorides