In Situ Functionalisation in Nitroxide Mediated Polymerisation: A Novel Extension towards Reversible Addition-Fragmentation Chain Transfer Polymerisation and Thiol-Ene Chemistry

LIONEL PETTON; ANDRÉS E. CIOLINO; MILAN M. STAMENOVIÆ; PIETER ESPEEL; FILIP E. DU PREZ

MACROMOLECULAR RAPID COMMUNICATIONS

WILEY-V C H VERLAG GMBH

Lugar: Weinheim; Año: 2012 vol. 33 p. 1310 - 1315

1022-1336

A straightforward, novel strategy based on the in situ functionalization of polymers prepared by nitroxide-mediated polymerization (NMP), for the use as an extension toward block copolymers and post-polymerization modifications, has been investigated. The nitroxide end group is exchanged for a thiocarbonylthio end group by a rapid transfer reaction with bis(thiobenzoyl) disulfide to generate in situ reversible addition?fragmentation chain transfer (RAFT) macroinitiators. Moreover, not only have these macroinitiators been used in chain extension and block copolymerization experiments by the RAFT process but also a thiol-terminated polymer is synthesized by aminolysis of the RAFT end group and subsequently reacted with dodecyl vinyl ether by thiol-ene chemistry.