Journal ArticleDOI
Origin of Inhibition Effects in the Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization of Methyl Acrylate
TLDR
In this article, the reversible addition fragmentation chain transfer (RAFT) bulk polymerization of a fast propagating monomer (methyl acrylate, MA) has been studied using 1-phenylethyl dithiobenzoate (1-PEDB) and 2-(2-cyanopropyl) dithiopropyl (CPDB) as RAFT agents at 60 °C.Abstract:
The reversible addition fragmentation chain transfer (RAFT) bulk polymerization of a fast propagating monomer (methyl acrylate, MA) has been studied using 1-phenylethyl dithiobenzoate (1-PEDB) and 2-(2-cyanopropyl) dithiobenzoate (CPDB) as RAFT agents at 60 °C. Rate retardation with increasing initial RAFT agent concentrations is common to both 1-PEDB- and CPDB-mediated MA polymerizations and occurs in comparable magnitude. A pronounced inhibition period is observed in 1-PEDB-mediated MA polymerizations, whereas the corresponding CPDB-mediated polymerizations show considerably less inhibition. The cause for this inhibition may either be associated with the leaving group of the initial RAFT agent or with the slow fragmentation of the initial intermediate macroRAFT radical. The present experimental data suggest that slow fragmentation is the probable cause for inhibition. We conclude that the radical intermediate formed by addition of radicals to the initial RAFT agent is different in stability than the macroRAFT radical formed analogously from macroRAFT agent. The inhibition period is effectively reduced by the use of CPDB as the initial RAFT agent in methyl acrylate polymerizations.read more
Citations
More filters
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
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.
Journal ArticleDOI
Bioapplications of RAFT polymerization.
TL;DR: The control of molecular weight and molecular weight distribution has enabled access to complex architectures and site specific functionality that were previously impossible to achieve via traditional free radical polymerizations.
References
More filters
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.
Journal ArticleDOI
Controlled/"living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes
Journal ArticleDOI
Polymerization of Methyl Methacrylate with the Carbon Tetrachloride/Dichlorotris- (triphenylphosphine)ruthenium(II)/Methylaluminum Bis(2,6-di-tert-butylphenoxide) Initiating System: Possibility of 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-