Living Polymers by the Use of Trithiocarbonates as Reversible Addition−Fragmentation Chain Transfer (RAFT) Agents:  ABA Triblock Copolymers by Radical Polymerization in Two Steps

Mayadunne, Roshan T. A.; Rizzardo, Ezio; Chiefari, John; Krstina, Julia; Moad, Graeme; Postma, Almar; Thang, San H.

doi:10.1021/ma991451a

Cited by 462 publications

(400 citation statements)

References 12 publications

(23 reference statements)

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“…For unsymmetrical trithiocarbonates [96] and xanthates [57] two possible fragmentation pathways are possible.…”

Section: Side Reactions In Raftmentioning

confidence: 99%

“…The potential of this chemistry to cleave end groups and decolourize polymers and produce polymers with thiol end groups was cited in our initial communication on RAFT polymerization. [13] Examples of end-group cleavage with nucleophiles such as amines, [15,96,198,199] hydroxide, [93] and borohydride [164,200] can be found in recent publications. Radical induced reduction with, for example, tri-n-butylstannane [15,201,202] can be used to replace the thiocarbonylthio group with hydrogen.…”

Section: Bu 3 Snhmentioning

confidence: 99%

“…S, [14,46,96] AA, [63,97] MA [96] S-MAH [98] S 55 S 96 - [99] AA, [99] HEA, [99] EA, [99] AA-b-EA, S-b-AA, BA, [99,100] (MMA), [99] AM [73] EHA-b-EA [99] NC 58 [46] H 3 C-S---S, [6,46,96] MA, [6,96] MMA [6,96] - [15,101] BA [101] -…”

mentioning

confidence: 99%

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Living Radical Polymerization by the RAFT Process

Moad¹,

Rizzardo²,

Thang³

2005

Aust. J. Chem.

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2,134

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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“…For unsymmetrical trithiocarbonates [96] and xanthates [57] two possible fragmentation pathways are possible.…”

Section: Side Reactions In Raftmentioning

confidence: 99%

Section: Bu 3 Snhmentioning

confidence: 99%

See 1 more Smart Citation

Living Radical Polymerization by the RAFT Process

Moad¹,

Rizzardo²,

Thang³

2005

Aust. J. Chem.

Self Cite

2,134

1,894

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show abstract

“…[2] Thiocarbonylthio groups undergo reaction with nucleophiles and ionic reducing agents (e.g. amines, [8][9][10][11][12][13][14][15] hydroxide, [16,17] borohydride [18,19] ) to provide thiols. They also react with various oxidizing agents (including NaOCl, H 2 O 2 , Bu t OOH, peracids, ozone) [2,[20][21][22] and are sensitive to UV irradiation.…”

Section: Introductionmentioning

confidence: 99%

Thermolysis of RAFT-Synthesized Poly(Methyl Methacrylate)

et al. 2006

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Thermolysis provides a simple and efficient way of eliminating thiocarbonylthio groups from RAFT-synthesized polymers. The course of thermolysis of poly(methyl methacrylate) (PMMA) prepared with dithiobenzoate and trithiocarbonate RAFT agents was followed by thermogravimetric analysis (TGA), 1 H NMR spectroscopy, and gel permeation chromatography (GPC). The weight loss profile observed depends strongly on the RAFT agent used during polymer synthesis. PMMA with a methyl trithiocarbonate end group undergoes loss of that end group at ∼180 • C, at least in part, by a mechanism believed to involve homolysis of the C-CS 2 SCH 3 bond and subsequent depropagation. In contrast, PMMA with a dithiobenzoate end appears more stable. Only the end group is lost at ∼180 • C and the dominant mechanism is proposed to be a concerted elimination process analogous to that involved in the Chugaev reaction.

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“…The block copolymers were synthesized by a combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and 'click' chemistry. RAFT polymerization [84][85][86][87][88][89] is a commonly used 'living' free-radical polymerization technique that is well suited to polar and ionic monomers. Employed with the widely used 'click' coupling chemistry [90][91][92][93], the RAFT-'click' combination is a powerful tool for synthesizing block copolymers [94][95][96].…”

Section: Synthesis Of Block Copolymersmentioning

confidence: 99%

Designing nanostructured block copolymer surfaces to control protein adhesion

Schricker

Palacio

Bhushan

2012

Phil. Trans. R. Soc. A.

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The profile and conformation of proteins that are adsorbed onto a polymeric biomaterial surface have a profound effect on its in vivo performance. Cells and tissue recognize the protein layer rather than directly interact with the surface. The chemistry and morphology of a polymer surface will govern the protein behaviour. So, by controlling the polymer surface, the biocompatibility can be regulated. Nanoscale surface features are known to affect the protein behaviour, and in this overview the nanostructure of self-assembled block copolymers will be harnessed to control protein behaviour. The nanostructure of a block copolymer can be controlled by manipulating the chemistry and arrangement of the blocks. Random, A-B and A-B-A block copolymers composed of methyl methacrylate copolymerized with either acrylic acid or 2-hydroxyethyl methacrylate will be explored. Using atomic force microscopy (AFM), the surface morphology of these block copolymers will be characterized. Further, AFM tips functionalized with proteins will measure the adhesion of that particular protein to polymer surfaces. In this manner, the influence of block copolymer morphology on protein adhesion can be measured. AFM tips functionalized with antibodies to fibronectin will determine how the surfaces will affect the conformation of fibronectin, an important parameter in evaluating surface biocompatibility.

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Living Polymers by the Use of Trithiocarbonates as Reversible Addition−Fragmentation Chain Transfer (RAFT) Agents: ABA Triblock Copolymers by Radical Polymerization in Two Steps

Cited by 462 publications

References 12 publications

Living Radical Polymerization by the RAFT Process

Living Radical Polymerization by the RAFT Process

Thermolysis of RAFT-Synthesized Poly(Methyl Methacrylate)

Designing nanostructured block copolymer surfaces to control protein adhesion

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