Quantum-chemical studies of RAFT polymerization: methodology, structure-reactivity correlations and kinetic implications

Michelle Coote, Elizabeth Krenske, Ekaterina Pas

Research output: Chapter in Book/Report/Conference proceedingChapter (Book)Researchpeer-review

15 Citations (Scopus)


Controlled/living free-radical polymerization techniques such as reversible additiona??fragmentation chain transfer (RAFT) [1, 2] rely upon a kinetic strategy for controlling the molecular weight and architecture of the resulting polymer. Rather than eliminating the radicala??radical terminations entirely, their frequency is instead minimized with respect to the number of growing polymer chains through the reversible trapping of the growing polymeric radical as a dormant species. In the RAFT process this is achieved using dithioester compounds, known as RAFT agents. The propagating radical adds to the thiocarbonyl sulfur center of the dithioester to produce an intermediate carbon-centered radical. This carboncentered radical can then undergo I?-scission, either to re-form the propagating radical or to liberate a new carbon-centered radical (the a??leaving groupa??) (equation 2.1).
Original languageEnglish
Title of host publicationHandbook of RAFT Polymerization
EditorsChristopher Barner-Kwollik
Place of PublicationWeinheim Germany
PublisherJohn Wiley & Sons
Number of pages45
ISBN (Print)9783527319244
Publication statusPublished - 16 Sept 2008
Externally publishedYes


  • Kinetic implications
  • Methodology
  • Quantum-chemical studies
  • RAFT polymerization
  • Structure-reactivity correlations

Cite this