Hydrolytic Susceptibility of Dithioester Chain Transfer Agents and Implications in Aqueous RAFT Polymerizations

Thomas, David B.; Convertine, Anthony J.; Hester, Roger D.; Lowe, Andrew B.; McCormick, Charles L.

doi:10.1021/ma035572t

Cited by 231 publications

(239 citation statements)

References 31 publications

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“…However, care should be taken because certain RAFT agents show some hydrolytic sensitivity. [243] We have found that this roughly correlates with activity of the RAFT agent (dithiobenzoates > trithiocarbonates ≈ aliphatic dithioesters).…”

Section: Reaction Conditions (Temperature Pressure Solvent Lewis Amentioning

confidence: 73%

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: Reaction Conditions (Temperature Pressure Solvent Lewis Amentioning

confidence: 73%

Living Radical Polymerization by the RAFT Process

Moad¹,

Rizzardo²,

Thang³

2005

Aust. J. Chem.

2,128

1,894

View full text Add to dashboard Cite

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“…[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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“…These side reactions include hydrolysis of the monomer to form ammonia, which causes unwanted aminolysis of the CTAs, slow polymerisation rate and poor monomer conversion (< 28%). [35][36][37] Aiming to minimise such side reactions, we opted for a trithiocarbonate CTA, PABTC, to mediate the polymerization, as it has better hydrolytic stability even at temperatures as high as 70 °C, 24 and the polymerisations were undertaken in 40% in volume dioxane, in order to limit AAm hydrolysis. Furthermore, dioxane also facilitates the solubilisation of both PABTC and styrene monomer at the chain extension Conversion and DP of styrene were determined from 1 H-NMR in situ ( Figure S4).…”

Section: Ultraviolet-visible (Uv-mentioning

confidence: 99%

Preparation of Inert Polystyrene Latex Particles as MicroRNA Delivery Vectors by Surfactant-Free RAFT Emulsion Polymerization

et al. 2016

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Permanent WRAP URL:http://wrap.warwick.ac.uk/83846 Copyright and reuse:The Warwick Research Archive Portal (WRAP) makes this work by researchers of the University of Warwick available open access under the following conditions. Copyright © and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable the material made available in WRAP has been checked for eligibility before being made available.Copies of full items can be used for personal research or study, educational, or not-for profit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. Publisher's statement:This document is the Accepted Manuscript version of a Published Work that appeared in final form in Biomacromolecules, copyright © American Chemical Society after peer review and technical editing by the publisher.To access the final edited and published work see http://dx.doi.org/10.1021/acs.biomac.5b01633 A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP url' above for details on accessing the published version and note that access may require a subscription. AbstractWe present the preparation of 11 nm polyacrylamide-stabilised polystyrene latex particles for conjugation to a microRNA model by surfactant-free RAFT emulsion polymerisation. Our synthetic strategy involved the preparation of amphiphilic polyacrylamide-block-polystyrene copolymers, which were able to self-assemble into polymeric micelles and 'grow' into polystyrene latex particles. The surface of these sterically stabilised particles was postmodified with a disulfide-bearing linker for the attachment of the microRNA model, which can be released from the latex particles under reducing conditions. These nanoparticles offer the advantage of ease of preparation via a scaleable process, and the versatility of their synthesis makes them adaptable to a range of applications.

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Hydrolytic Susceptibility of Dithioester Chain Transfer Agents and Implications in Aqueous RAFT Polymerizations

Cited by 231 publications

References 31 publications

Living Radical Polymerization by the RAFT Process

Living Radical Polymerization by the RAFT Process

Thermolysis of RAFT-Synthesized Poly(Methyl Methacrylate)

Preparation of Inert Polystyrene Latex Particles as MicroRNA Delivery Vectors by Surfactant-Free RAFT Emulsion Polymerization

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