RAFT Polymerization – Then and Now

Moad, Graeme

doi:10.1021/bk-2015-1187.ch012

Cited by 49 publications

(29 citation statements)

References 201 publications

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“…Note that the proposed multi-rate multi-delay observer is based on the continuous reduced-order observer (5). It has been proved that, as long as the maximum sampling period satisfies a certain limit, the stability of error dynamics for the continuous observer of (5) implies the validity of the multi-rate multi-delay observer [56].…”

Section: Prediction Of Raft Polymerizationmentioning

confidence: 99%

Modeling and Observer-Based Monitoring of RAFT Homopolymerization Reactions

et al. 2019

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Reversible addition–fragmentation chain–transfer (RAFT) polymerization of methyl methacrylate (MMA) is modeled and monitored using a multi-rate multi-delay observer in this work. First, to fit the RAFT reaction rate coefficients and the initiator efficiency in the model, in situ 1 H nuclear magnetic resonance (NMR) experimental data from small-scale (<2 mL) NMR tube reactions is obtained and a least squares optimization is performed. 1 H NMR and size exclusion chromatography (SEC) experimental data from large-scale (>400 mL) reflux reactions is then used to validate the fitted model. The fitted model accurately predicts the polymer properties of the large-scale reactions with slight discordance at late reaction times. Based on the fitted model, a multi-rate multi-delay observer coupled with an inter-sample predictor and dead time compensator is designed, to account for the asynchronous multi-rate measurements with non-constant delays. The multi-rate multi-delay observer shows perfect convergence after a few sampling times when tested against the fitted model, and is in fair agreement with the real data at late reaction times when implemented based on the experimental measurements.

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Section: Prediction Of Raft Polymerizationmentioning

confidence: 99%

Modeling and Observer-Based Monitoring of RAFT Homopolymerization Reactions

et al. 2019

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“…And the process can be pursued if so desired. This so-called RAFT/MADIX technology has proved extremely powerful, as can be judged from the large number of publications and patents related to it [63]. Almost any desired polymeric architecture can be assembled and the process is easily implemented on an industrial scale.…”

Section: Scheme 22mentioning

confidence: 99%

Some aspects of radical cascade and relay reactions

Quiclet‐Sire¹,

Zard²

2017

Proc. R. Soc. A.

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The ability to create carbon-carbon bonds is at the heart of organic synthesis. Radical processes are particularly apt at creating such bonds, especially in cascade or relay sequences where more than one bond is formed, allowing for a rapid assembly of complex structures. In the present brief overview, examples taken from the authors' laboratory will serve to illustrate the strategic impact of radical-based approaches on synthetic planning. Transformations involving nitrogen-centred radicals, electron transfer from metallic nickel and the reversible degenerative exchange of xanthates will be presented and discussed. The last method has proved to be a particularly powerful tool for the intermolecular creation of carbon-carbon bonds by radical additions even to unactivated alkenes. Various functional groups can be brought into the same molecule in a convergent manner and made to react together in order to further increase the structural complexity. One important benefit of this chemistry is the so-called RAFT/MADIX technology for the manufacture of block copolymers of almost any desired architecture.

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“…It is a powerful method for the preparation of a diverse range of polymer architectures with narrow molar mass distributions, and well‐defined end‐groups and compositions . While the impact of thiocarbonylthio RAFT polymerization has been widespread, some limitations still exist with respect to scope and utility of individual agents . The dithiocarbamates are a versatile class of RAFT agents with widespread applicability with respect to monomer type .…”

Section: Introductionmentioning

confidence: 99%

4-Halogeno-3,5-dimethyl-1H-pyrazole-1-carbodithioates: versatile reversible addition fragmentation chain transfer agents with broad applicability

et al. 2017

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Pyrazole-based dithiocarbamates are versatile reversible addition fragmentation chain transfer (RAFT) agents that provide molar mass and dispersity (Ð) control over the radical polymerization of both more and less activated monomers (MAMs and LAMs). In this paper we report on theoretical and experimental findings demonstrating that their activity as RAFT agents can be significantly enhanced by introducing electron-withdrawing substituents to the pyrazole ring. This enhancement is most noticeable in methyl methacrylate polymerization where product molar masses are more accurately predicted by the RAFT agent concentration, and significantly lower Ð values, with respect to those seen with the parent RAFT agent under similar conditions, are observed. Thus, use of 4-chloro-3,5-dimethyl-1H-pyrazole-1-carbodithioate provides a poly(methyl methacrylate) with the anticipated molar mass and Ð as low as 1.3 at high monomer conversion. Good control is retained for monosubstituted MAMs, styrene, methyl acrylate and N,N-dimethylacrylamide. Low dispersities and less molar mass control are also achieved for homoand copolymerizations with the LAM vinyl acetate, albeit with some retardation.

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RAFT Polymerization – Then and Now

Cited by 49 publications

References 201 publications

Modeling and Observer-Based Monitoring of RAFT Homopolymerization Reactions

Modeling and Observer-Based Monitoring of RAFT Homopolymerization Reactions

Some aspects of radical cascade and relay reactions

4-Halogeno-3,5-dimethyl-1H-pyrazole-1-carbodithioates: versatile reversible addition fragmentation chain transfer agents with broad applicability

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