The future of reversible addition fragmentation chain transfer polymerization

Barner‐Kowollik, Christopher; Perrier, Sébastien

doi:10.1002/pola.22866

Cited by 278 publications

(190 citation statements)

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“…Work cited in the previous reviews [7,8] is only mentioned again where necessary to put the more recent work in context. The past 2 years has seen the publication of further general reviews detailing the RAFT process which include works by Moad, Rizzardo, and Thang, [9][10][11][12] a Handbook of RAFT Polymerization, [13] and a highlight article by Barner-Kowollik and Perrier [14] on the future of RAFT. Reviews on specific areas include the kinetics and mechanism of RAFT polymerization, [15][16][17][18] the use of RAFT to probe the kinetics of radical polymerization, [19,20] the use of RAFT in organic synthesis, [21] amphiphilic block copolymer synthesis, [22,23] the synthesis of end functional polymers, [24] the synthesis of star polymers and other complex architectures, [25,26] the use of trithiocarbonate RAFT agents, [27] the use of xanthate RAFT agents (MADIX), [28] polymerization in heterogeneous media, [29][30][31][32] RAFT polymerization initiated with ionizing radiation, [33] polymer synthesis in aqueous solution, [34][35][36][37] surface and particle modification, [38,39] synthesis of self assembling and/or stimuli responsive polymers, [36,40] RAFT-synthesized polymers in drug delivery, [22,41] and other applications of RAFTsynthesized polymers.…”

Section: San H Thang Completed His Bsc (Hons) In 1983 and Phd Inmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process - A Second Update

Moad¹,

Rizzardo²,

Thang³

2009

Aust. J. Chem.

902

720

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This paper provides a second update to the review of reversible deactivation radical polymerization achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of reversible addition-fragmentation chain transfer (RAFT) that was published in June 2005 (Aust. J. Chem. 2005, 58, 379-410). The first update was published in November 2006 (Aust. J. Chem. 2006, 59, 669-692). This review cites over 500 papers that appeared during the period mid-2006 to mid-2009 covering various aspects of RAFT polymerization ranging from reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses and a diverse range of applications. Significant developments have occurred, particularly in the areas of novel RAFT agents, techniques for end-group removal and transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

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Section: San H Thang Completed His Bsc (Hons) In 1983 and Phd Inmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process - A Second Update

Moad¹,

Rizzardo²,

Thang³

2009

Aust. J. Chem.

902

720

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“…We present a protocol appropriate for flow microreactors to perform in situ aminolysis of polymers obtained from the reversible addition fragmentation transfer (RAFT) process 13 followed by basecatalysed thiol-ene end group modification, a reaction that is sometimes referred to as belonging to the click-type reactions.…”

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confidence: 99%

Use of a continuous-flow microreactor for thiol–ene functionalization of RAFT-derived poly(butyl acrylate)

Vandenbergh

Junkers

2012

Polym. Chem.

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This study describes the synthesis of functionalized RAFT-derived poly(n-butyl acrylate) polymers via the use of a continuous-flow microreactor, in which aminolysis as well as thiol-ene reactions are executed in reaction times of just 20 minutes. Poly(n-butyl acrylate) (M n ¼ 3800 g mol À1, PDI ¼ 1.10) with a trithiocarbonate end group was prepared via a conventional RAFT process. The polymer was then functionalized via aminolysis/thiol-ene reactions in the micro-flow reactor with isobornyl acrylate, propargyl acrylate, poly(ethylene glycol) methyl ether acrylate and pentaerythritol tetraacrylate. To optimize the reaction time and reaction temperature of the micro-flow reactor, freshly collected samples were studied with soft ionization mass spectrometry. With this technique, efficient and very fast aminolysis and subsequent thiol-ene reactions take place on the RAFT-precursor polymer, yielding quantitative end group conversion within 20 min and functionalized polymers of 3700-4000 g mol À1, depending on the type of acrylate coupled. The use of a continuous-flow microreactor opens the pathway towards upsizing lab scale methods into larger processes without suffering from problems associated with reproducibility and tedious optimization issues.An often less valued key aspect of contemporary polymer synthesis, be it in the realm of controlled polymerization, click-like modifications or polymer analogous reactions, is the ability to upscale existing synthesis protocols. The adaption of procedures from microgram scale to significant production of materials on gram scale or larger is often tedious and accompanied with a loss in reaction efficiency or unreasonable reaction volumes. A convenient solution to this problem is the employment of microreactor technology.1 Miniaturized flow reactors offer the ability to optimize reaction conditions on a small scale while concomitantly allowing for simple upscale of reactions by going from small reactors to massive parallelization in reactor arrays or simply longer runtimes of the individual reactors. Also accelerations of the reactions can often be achieved by the rapid mixing of the components due to short diffusion lengths inside the microreactor, 2 as well as employing unconventional temperature regimes making microreactors in that respect comparable to the use of microwave reactors. The improved heat transfer of microreactors is a distinct advantage of these devices making their use especially interesting for highly exothermic reactions.3 While a wide array of commercial microreactors already exists, only a few studies have been reported so far on applications from the polymer field. Recently, Bally et al. described the synthesis of branched polymers from atom transfer radical polymerization (ATRP), 4 in a tubular microreactor. 5Also, polymerizations following the reversible addition fragmentation transfer (RAFT) 6 protocol have been described lately 7,8 as well as end group modifications 9 . Some earlier work on polymerizations in flow microreactors is summarized in a re...

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“…In particular, advances in living radical polymerization [1][2][3] have enabled a much broader range of functional groups to be incorporated into copolymer structures than was previously possible using anionic polymerization. [4] Well-defined block copolymer amphiphiles undergo self-assembly in aqueous solution in order to minimize energetically unfavourable hydrophobe-water interactions.…”

Section: Introductionmentioning

confidence: 99%

Self‐Assembled Block Copolymer Aggregates: From Micelles to Vesicles and their Biological Applications

Blanazs

Armes

Ryan

2009

Macromol. Rapid Commun.

1,392

1,370

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The ability of amphiphilic block copolymers to self‐assemble in selective solvents has been widely studied in academia and utilized for various commercial products. The self‐assembled polymer vesicle is at the forefront of this nanotechnological revolution with seemingly endless possible uses, ranging from biomedical to nanometer‐scale enzymatic reactors. This review is focused on the inherent advantages in using polymer vesicles over their small molecule lipid counterparts and the potential applications in biology for both drug delivery and synthetic cellular reactors.magnified image

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The future of reversible addition fragmentation chain transfer polymerization

Cited by 278 publications

References 28 publications

Living Radical Polymerization by the RAFT Process - A Second Update

Living Radical Polymerization by the RAFT Process - A Second Update

Use of a continuous-flow microreactor for thiol–ene functionalization of RAFT-derived poly(butyl acrylate)

Self‐Assembled Block Copolymer Aggregates: From Micelles to Vesicles and their Biological Applications

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