RAFT in Emulsion Polymerization: What Makes it Different?

Prescott, Stuart W.; Ballard, Mathew J.; Rizzardo, Ezio; Gilbert, Robert G.

doi:10.1071/ch02073

Cited by 127 publications

(135 citation statements)

References 60 publications

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“…[9] Much research has shown that the success in RAFT emulsion polymerization depends strongly on the choice of RAFT agent and polymerization conditions. [9,[175][176][177][178][179][180][181][182][183] Most work has focussed on styrene polymerization, [9,176,177,183] although RAFT emulsion polymerizations of BA [178] and methcrylates [9,13] have also been reported. Use of cumyl dithiobenzoate 22 as RAFT agent in ab initio emulsion polymerization of styrene is not recommended.…”

Section: Raft In Heterogeneous Mediamentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process

Moad¹,

Rizzardo²,

Thang³

2005

Aust. J. Chem.

2,128

1,894

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This paper presents a review of living radical polymerization achieved with thiocarbonylthio compounds [ZC( S)SR] by a mechanism of reversible addition-fragmentation chain transfer (RAFT). Since we first introduced the technique in 1998, the number of papers and patents on the RAFT process has increased exponentially as the technique has proved to be one of the most versatile for the provision of polymers of well defined architecture. The factors influencing the effectiveness of RAFT agents and outcome of RAFT polymerization are detailed. With this insight, guidelines are presented on how to conduct RAFT and choose RAFT agents to achieve particular structures. A survey is provided of the current scope and applications of the RAFT process in the synthesis of well defined homo-, gradient, diblock, triblock, and star polymers, as well as more complex architectures including microgels and polymer brushes.

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Section: Raft In Heterogeneous Mediamentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process

Moad¹,

Rizzardo²,

Thang³

2005

Aust. J. Chem.

2,128

1,894

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“…We have discussed these challenges in our contributions to this topic [78][79][80] and in our comprehensive reviews of the RAFT process. [81][82][83] RAFT polymerization can be initiated by any source of free radicals including UV irradiation [84] and gamma irradiation [85] and can be performed over a wide range of temperatures, including room temperature.…”

Section: Thiocarbonyl Class Of Afctasmentioning

confidence: 99%

On the Origins of Nitroxide Mediated Polymerization (NMP) and Reversible Addition–Fragmentation Chain Transfer (RAFT)

Rizzardo¹,

Solomon²

2012

Aust. J. Chem.

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The early experiments on radical polymerization, which were to lead to a study of nitroxide trapping of the initiation step and the interest in defect groups, particularly the macromonomers formed by termination by disproportionation, are discussed. Results from the nitroxide trapping clearly show that the initiation step ranges from simple clean addition to the head of the monomer, to complex addition/abstraction reactions. Careful selection of the monomer/initiation system is emphasized with particular reference to two common monomers, styrene and methyl methacrylate, and two initiating radicals, t-butoxy and benzoyloxy. The discovery of nitroxide mediated polymerization (NMP) from observations made during the nitroxide trapping work is reported and the ability to have a living radical system demonstrated with numerous examples. Similarly, the study of the copolymerization of macromonomers, formed by disproportionation of the propagating chains, is discussed with the discovery of b-scission and an early form of addition-fragmentation reported. The evolution of reversible addition-fragmentation chain transfer (RAFT) to a highly versatile and commercially attractive radical system is reported and the detailed chemistry behind the discovery of this living radical system discussed. Both NMP and RAFT enable the synthesis of structures not previously possible by radical polymerization and in some cases not possible by any other process.

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“…(mini)emulsion), without issues related to colloidal instability. 5,7,[44][45][46][47] A key feature is the xanthate surface activity, which allows the synthesis of covalently linked core-shell nanoparticles with typically styrene as the core. 30,33,48 Be that as it may, exit/entry and even re-entry phenomena can disturb the desired growth so that the identification of the most suited conditions is non-trivial.…”

Section: Introductionmentioning

confidence: 99%