Journal ArticleDOI
Thiocarbonylthio Compounds [SC(Ph)S−R] in Free Radical Polymerization with Reversible Addition-Fragmentation Chain Transfer (RAFT Polymerization). Role of the Free-Radical Leaving Group (R)
TLDR
In this paper, the effect of substituents R of dithiobenzoate RAFT agents [SC(Ph)S−R] on the outcome of polymerizations of styrene, methyl methacrylate (MMA), and butyl (BA) or methyl acrylate(MA).Abstract:
Radical polymerization with reversible addition−fragmentation chain transfer (RAFT polymerization) can be used to synthesize a wide range of polymers of controlled architecture and narrow molecular weight distribution. The polymerizations use addition−fragmentation chain transfer agents (RAFT agents) that possess high transfer coefficients in free radical polymerization and confer living character on the polymerization. This paper explores the effect of the substituents R of dithiobenzoate RAFT agents [SC(Ph)S−R] on the outcome of polymerizations of styrene, methyl methacrylate (MMA) and butyl (BA) or methyl acrylate (MA). In MMA polymerization at 60 °C, effectiveness depends strongly on R decreasing in the order where R is: −C(Alkyl)2CN ∼ −C(Me)2Ar > −C(Me)2C(O)O(alkyl) > −C(Me)2C(O)NH(alkyl) > −C(Me)2CH2C(Me)3 ≥ −C(Me)HPh > −C(Me)3 ∼ −CH2Ph. Of these, only the compounds with R = −C(Me)2Ph and −C(Me)2CN provided polymers with substantially narrowed polydispersities in batch polymerization and gave molec...read more
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Journal ArticleDOI
Controlled/living radical polymerization: Features, developments, and perspectives
TL;DR: In this article, a review of recent mechanistic developments in the field of controlled/living radical polymerization (CRP) is presented, with particular emphasis on structure-reactivity correlations and "rules" for catalyst selection in ATRP, for chain transfer agent selection in reversible addition-fragmentation chain transfer (RAFT) polymerization, and for the selection of an appropriate mediating agent in stable free radical polymerisation (SFRP), including organic and transition metal persistent radicals.
Journal ArticleDOI
Living radical polymerization by the RAFT process
TL;DR: A review of living radical polymerization achieved with thiocarbonylthio compounds by a mechanism of reversible addition-fragmentation chain transfer (RAFT) is presented in this article.
Journal ArticleDOI
Living Radical Polymerization by the RAFT Process - A Second Update
TL;DR: The authors provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(S)SR) by a mechanism of reversible addition-fragmentation chain transfer (RAFT) that was published in June 2005.
Journal ArticleDOI
Radical addition-fragmentation chemistry in polymer synthesis
TL;DR: In this paper, a review of the development of addition-fragmentation chain transfer agents and related ring-opening monomers highlighting recent innovation in these areas is presented, including dithioesters, trithiocarbonates, dithioco-baramates and xanthates.
Journal ArticleDOI
Macromolecular design via réversible addition-fragmentation chain transfer (RAFT)/Xanthates (MADIX) polymerization
TL;DR: A review of the progress made in reversible addition-fragmentation chain transfer (RAFT) and macromolecular design via the interchange of xanthates (MADIX) polymerization can be found in this article.
References
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Journal ArticleDOI
Living free-radical polymerization by reversible addition - Fragmentation chain transfer: The RAFT process
John Chiefari,Y. K. Chong,Frances Ercole,Julia Krstina,Justine Leigh Jeffery,Tam P. T. Le,Roshan T. A. Mayadunne,Gordon Francis Meijs,Catherine Louise Moad,Graeme Moad,Ezio Rizzardo,San H. Thang +11 more
TL;DR: The authors proposed a reversible additive-fragmentation chain transfer (RAFT) method for living free-radical polymerization, which can be used with a wide range of monomers and reaction conditions and in each case it provides controlled molecular weight polymers with very narrow polydispersities.
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New polymer synthesis by nitroxide mediated living radical polymerizations.
Journal ArticleDOI
Metal-catalyzed living radical polymerization.
Journal ArticleDOI
Living free radical polymerization with reversible addition : fragmentation chain transfer (the life of RAFT)
Graeme Moad,John Chiefari,Y. K. Chong,Julia Krstina,Roshan T. A. Mayadunne,Almar Postma,Ezio Rizzardo,San H. Thang +7 more
TL;DR: In this article, free radical polymerization with reversible addition-fragmentation chain transfer (RAFT polymerization) is discussed with a view to answering the following questions: (a) How living is RAFT polymerization? (b) What controls the activity of thiocarbonylthio compounds in RAFT polymers, and (c) How do rates of polymerization differ from those of conventional radical polymerisation? (d) Can RAFT agents be used in emulsion polymerization; and (e) Retardation, observed when high concentra-