Fast and Complete Neutralization of Thiocarbonylthio Compounds Using Trialkylborane and Oxygen: Application to Their Removal from RAFT-Synthesized Polymers.

A rapid and efficient method to remove thiocarbonylthio end groups from polymers prepared by reversible addition-fragmentation chain transfer (RAFT) is described. The elimination process is obtained in less than 1 min by treating the solution of RAFT-synthesized polymers with 5 equiv of trialkylborane (TAB) in the presence of oxygen under an ambient temperature. The versatility of this method was checked on the most relevant families of thiocarbonylthio chain transfer agents (CTA), including dithioesters, trithiocarbonates, dithiocarbamates, and xanthates, carried by the corresponding RAFT-synthesized polymers. UV, NMR, and MALDI-TOF MS characterization results all confirm the complete removal of their terminal CTA groups.