Addition-Fragmentation Kinetics of Fluorodithioformates (F-RAFT) in Styrene, Vinyl Acetate, and Ethylene Polymerization:  An Ab Initio Investigation

Coote, Michelle L.; Izgorodina, Ekaterina I.; Cavigliasso, Germán; Roth, Marion; Busch, Markus; Barner‐Kowollik, Christopher

doi:10.1021/ma060470z

Cited by 55 publications

(52 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…101,102 It is also worth noting that ab initio investigations have suggested the use of fluorine as the stabilizing Z group can afford CTAs that may also be capable of successfully mediating the polymerization of monomers with disparate reactivity. 103,104 However, to date, this possibility has been only rarely explored, perhaps as a result of the rather challenging synthesis required to obtain CTAs with fluorine Z groups.…”

Section: Monomer Class Specificity Of Raft Agentsmentioning

confidence: 99%

Expanding the Scope of RAFT Polymerization: Recent Advances and New Horizons

2015

View full text Add to dashboard Cite

Reversible deactivation radical polymerization (RDRP) has revolutionized modern polymer chemistry over the past two decades, thus laying the groundwork for the synthesis of complex macromolecules and enabling the preparation of previously inaccessible materials. Reversible addition-fragmentation chain transfer (RAFT) polymerization has emerged as one of the most promising techniques because of its functional group tolerance, applicability to a wide range of vinyl monomers, and its nondemanding experimental conditions. However, despite the promise and clearly demonstrated utility of RAFT, limitations of the method sometimes still exist, including the occasional need for extended polymerization times, limited access to high molecular weight polymers, low "livingness" due to unavoidable radical termination events, etc. This Perspective focuses on recent advances that have been specifically designed to address many of these perceived limitations to reinforce the promise of RAFT for the synthesis of complex and well-defined polymers under facile conditions.

show abstract

Section: Monomer Class Specificity Of Raft Agentsmentioning

confidence: 99%

Expanding the Scope of RAFT Polymerization: Recent Advances and New Horizons

2015

View full text Add to dashboard Cite

show abstract

“…[36][37][38][39] Buback and co-workers [37] have reported what they term the SP-PLP-ESR-RAFT technique where the rate of build-up and decay of the intermediate following radical generation is followed by EPR spectroscopy and analyzed to provide addition and (overall) fragmentation rates. Coote and co-workers [9,32,33,[40][41][42][43] have devised methods for calculating absolute values of K by applying ab initio methods. Values of K have also been estimated on the basis of simulation of the polymerization kinetics.…”

Section: Choice Of Raft Agentsmentioning

confidence: 99%

“…On the basis of computational studies on RAFT agents, Z-C(=S)SR, a RAFT agent with Z = fluorine was proposed [40,43,47] as a 'universal' RAFT agent able to efficiently control the polymerization of both activated (e.g. acrylates, styrene) and less-activated monomers (e.g.…”

Section: Choice Of Raft Agentsmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process—A First Update

Moad¹,

Rizzardo²,

Thang³

2006

Aust. J. Chem.

858

787

View full text Add to dashboard Cite

This paper provides a first update to the review of living radical polymerization achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of Reversible Addition-Fragmentation chain Transfer (RAFT) published in June 2005. The time since that publication has witnessed an increased rate of publication on the topic with the appearance of well over 200 papers covering various aspects of RAFT polymerization ranging over reagent synthesis and properties, kinetics, and mechanism of polymerization, novel polymer syntheses, and diverse applications.

show abstract

“…On the basis of ab initio calculations Coote and coworkers proposed that fluorodithioformates (Z = F) should serve as universal RAFT agents, able to control the polymerization of S as well as VAc [95,96]. The fluoro substituent destabilizes the radical adduct, favoring fragmentation, without deactivating the C=S double bond towards radical addition.…”

Section: General Raft Agent Structurementioning

confidence: 99%

RAFT Polymerization of Vinyl Esters: Synthesis and Applications

et al. 2014

View full text Add to dashboard Cite

This article is the first comprehensive review on the study and use of vinyl ester monomers in reversible addition fragmentation chain transfer (RAFT) polymerization. It covers all the synthetic aspects associated with the definition of precision polymers comprising poly(vinyl ester) building blocks, such as the choice of RAFT agent and reaction conditions in order to progress from simple to complex macromolecular architectures. Although vinyl acetate was by far the most studied monomer of the range, many vinyl esters have been considered in order to tune various polymer properties, in particular, solubility in supercritical carbon dioxide (scCO 2 ). A special emphasis is given to novel poly(vinyl alkylate)s with enhanced solubilities in scCO 2 , with applications as reactive stabilizers for dispersion polymerization and macromolecular surfactants for CO 2 media. Other miscellaneous uses of poly(vinyl ester)s synthesized by RAFT, for instance as a means to produce poly(vinyl alcohol) with controlled characteristics for use in the biomedical area, are also covered.

show abstract

Addition-Fragmentation Kinetics of Fluorodithioformates (F-RAFT) in Styrene, Vinyl Acetate, and Ethylene Polymerization: An Ab Initio Investigation

Abstract: S=C(CH 3)SCH 3 1\1\GINC-AC19\FOpt\RB3LYP\6-31G(d)\C3H6S2\EXI501\30-Jan-2006\0\\#P GFI NPUT B3LYP/6-31G(D) INT(GRID=ULTRAFINE) OPT MAXDISK=268435456\\R=MA la rge BS\\0,

Cited by 55 publications

References 24 publications

Expanding the Scope of RAFT Polymerization: Recent Advances and New Horizons

Expanding the Scope of RAFT Polymerization: Recent Advances and New Horizons

Living Radical Polymerization by the RAFT Process—A First Update

RAFT Polymerization of Vinyl Esters: Synthesis and Applications

Contact Info

Product

Resources

About