Recent Advances in the Kinetics of Reversible Addition Fragmentation Chain-Transfer Polymerization

Vana, Philipp; Quinn, John F.; Davis, Thomas P.; Barner‐Kowollik, Christopher

doi:10.1071/ch02042

Cited by 77 publications

(99 citation statements)

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“…In this light, coupled with the evidence from kinetic studies of the induction period in RAFT polymerisation, [27,28] it seems likely that the ongoing discrepancy between the slow fragmentation model and the EPR-derived radical concentrations [5] lies not in a revision of the measured K values, but rather the introduction of additional side reactions involving the RAFT-adduct radical, such as reversible termination. [29,30] Further work in this direction is now underway.…”

Section: Discussionmentioning

confidence: 96%

Is the Addition‐Fragmentation Step of the RAFT Polymerisation Process Chain Length Dependent?

Izgorodina

Coote

2006

Macro Theory & Simulations

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Summary: The chain length dependence of the addition‐fragmentation equilibrium constant (K) for cumyl dithiobenzoate (CDB) mediated polymerisation of styrene has been studied via high level ab initio molecular orbital calculations. The results indicate that chain length and penultimate unit effects are extremely important during the early stages of the polymerisation process. In the case of the attacking radical (i.e., R• in: R• + SC(Z)SR′ → RSC•(Z)SR′), the equilibrium constant varies by over three orders of magnitude on extending R• from the styryl unimer to the trimer species and actually increases with chain length, further confirming that K is high in this system. When the reactions of the cumyl leaving group and cyanoisopropyl initiating species, which are also present in CDB‐mediated polymerisation of styrene in the presence of the initiator 2,2′‐azoisobutyronitrile, are also included, the variation in K extends over five orders of magnitude. Although less significant, the influence of the R′ group should also be taken into account in a complete kinetic model of the RAFT process. However, for most practical purposes, its chain length effects beyond the unimer stage may be ignored. These results indicate that current simplified models of the RAFT process, which typically ignore all chain length effects in the R and R′ positions, and all substituent effects in the R′ position, may be inadequate, particularly in modelling the initial stages of the process. magnified image

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Section: Discussionmentioning

confidence: 96%

Is the Addition‐Fragmentation Step of the RAFT Polymerisation Process Chain Length Dependent?

Izgorodina

Coote

2006

Macro Theory & Simulations

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“…Side reactions, like intermediate storage effects and intermediate termination reactions, [15] are not included and fragmentation (described by k Àb ) of the intermediate macroRAFT radical was assumed to be fast. As long as k Àb is large enough, radical storage effects will not play a role (i.e.…”

Section: Model Validationmentioning

confidence: 99%

Easy Access to Chain-Length-Dependent Termination Rate Coefficients Using RAFT Polymerization

Vana

Davis

Barner‐Kowollik

2002

Macromol. Rapid Commun.

107

123

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“…An The first output of that working party, being a dilemma paper that summarizes the current situation, has just been published. [25] It has been suggested at various times that the intermediates in the RAFT equilibria (2 and/or 4) might react reversibly with propagating radicals [26][27][28] and thus these species might be mediators of radical polymerization by a reversible termination mechanism.…”

Section: Mechanism Of Raftmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process—A First Update

Moad¹,

Rizzardo²,

Thang³

2006

Aust. J. Chem.

858

787

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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.

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Recent Advances in the Kinetics of Reversible Addition Fragmentation Chain-Transfer Polymerization

Cited by 77 publications

References 0 publications

Is the Addition‐Fragmentation Step of the RAFT Polymerisation Process Chain Length Dependent?

Is the Addition‐Fragmentation Step of the RAFT Polymerisation Process Chain Length Dependent?

Easy Access to Chain-Length-Dependent Termination Rate Coefficients Using RAFT Polymerization

Living Radical Polymerization by the RAFT Process—A First Update

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