Reversible addition–fragmentation chain‐transfer polymerization: Unambiguous end‐group assignment via electrospray ionization mass spectrometry

Abstract

Abstract Electrospray ionization mass spectrometry was performed to identify the structure of polymeric methyl acrylates generated via the cumyl dithiobenzoate (CDB), cumyl p ‐fluorodithiobenzoate (CPFDB), and 1‐phenylethyl dithiobenzoate (PEDB) mediated reversible addition–fragmentation chain‐transfer (RAFT) polymerizations. The relatively simple spectra clearly demonstrate the end groups of this living free‐radical polymerization technique. Only polymeric chains carrying one leaving group of the RAFT agent and the dithiobenzoate end group as the active RAFT center were discovered. Multiple‐stage mass spectrometric experiments and oxidation of the dithioester end group confirmed the structure of the generated polymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4032–4037, 2002