Reaction of Cyclic Tetrathiophosphates with Carboxylic Acids as a Means to Generate Dithioesters and Control Radical Polymerization By RAFT

Duréault, Alex; Gnanou, Yves; Taton, Daniel; Destarac, Mathias; Leising, Frédéric

doi:10.1002/ange.200250770

Cited by 19 publications

(24 citation statements)

References 14 publications

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“…These include the reaction of benzyl chloride [9,123] or a benzyl sulfone [124] with elemental sulfur in the presence of base, reaction of phenyl Grignard reagent with carbon disulfide, [9] and treatment of benzoic acid with P 4 S 10 or Davey reagent. [121,125] …”

Section: Synthesis Of Raft Agentsmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process

Moad¹,

Rizzardo²,

Thang³

2005

Aust. J. Chem.

2,150

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: Synthesis Of Raft Agentsmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process

Moad¹,

Rizzardo²,

Thang³

2005

Aust. J. Chem.

2,150

1,894

View full text Add to dashboard Cite

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“…[46][47][48][49][50][51][52][53] We have recently shown that dithioesters can be obtained in just one step from the reaction of P 4 S 10 (or Davy reagents) with a carboxylic acid in the presence of an alkyl bromide -or radical source -and can be used in situ to control free-radical polymerizations by a RAFT-type mechanism. 54 This report describes (i) the synthesis of multifunctional dithioesters using P 4 S 10 , a thiol (RSH), and a multicarboxylic acid precursor, and (ii) the subsequent utilization of these dithioesters to prepare ABA-type triblock copolymers and three-arm polystyrene stars by RAFT.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Multifunctional Dithioesters Using Tetraphosphorus Decasulfide and Their Behavior as RAFT Agents

et al. 2004

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The reaction of tetraphosphorus decasulfide (P4S10) with multicarboxylic acids and benzyl thiol afforded multifunctional dithioesters by a simple experimental procedure. The dithioesters were subsequently used as chain transfer agents to grow poly(tert-butylacrylate) and/or polystyrene chains in a controlled fashion by reversible addition-fragmentation chain transfer (RAFT). RAFT polymerizations of styrene were performed thermally at 110°C either in bulk or in toluene solution, while tert-butylacrylate was polymerized at 60°C in toluene in the presence of AIBN as the radical source. The multifunctional RAFT agents provided good control over the molar masses and polydispersities of the polymers formed, even though the presence of some linear dead chains generated by irreversible terminations could not be avoided. The contribution of the latter reactions was enhanced with the increase of viscosity at high conversion and with the "shielding effect" created by the polymeric arms around the RAFT centers of the core. Better control could be achieved when performing RAFT-mediated polymerizations in toluene solution as compared to bulk experiments. This methodology was applied to synthesize not only linear poly(tertbutylacrylate-b-styrene-b-tert-butylacrylate) triblock copolymers, but also three-arm polystyrene stars following an "arm-first" approach.

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“…The RAFT agent, cyanoisopropyl dithiobenzoate was synthesized and purified according to Duréault et al [30], by the reaction of phosphorus pentasulfide (Aldrich), AIBN, and benzoic acid (Fluka) in toluene (Merck). All the reactants for the synthesis of CPDB were used as received.…”

Section: Methodsmentioning

confidence: 99%