In-Situ NMR Spectroscopy for Probing the Efficiency of RAFT/MADIX Agents

Pound, Gwenaelle; McLeary, James B.; McKenzie, Jean M.; Lange, Ronald F. M.; Klumperman, Bert

doi:10.1021/ma061843z

Cited by 92 publications

(100 citation statements)

References 9 publications

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“…These rate constants are reflected in experimental results of RAFT polymerizations. Use of strongly stabilized R-groups such as 2-cyanoisopropyl [67,106] or α-(PEGoxycarbonyl) benzyl [107] result in near-total inhibition of VAc or VBz polymerization due to slow reinitiation. Good control over polymerization is obtained with 1-phenylethyl [72,108] though very long inhibition times (10-48 h) are observed.…”

Section: Methodsmentioning

confidence: 99%

“…In between these extremes, a wide range of R-groups may be employed to good effect, including esters of 1-acetyl [86][87][88][89][90]108,[110][111][112][113], 2-propionyl [3][4][5][6][7][8][9]30,31,34,66,69,70,[80][81][82]85,89,91,107,[114][115][116][117][118][119][120][121][122][123] and 2-methyl-2-propionyl [67,91], 2-acetic acid [124], 2-propionic acid [106,114,125], t-butyl [106], cyanomethyl [67,102], benzyl …”

Section: Methodsmentioning

confidence: 99%

“…In 2007, based on their previous work revealing the selective initialization in RAFT polymerization of VAc for specific leaving groups [106], Pound et al [107] modified commercial mono-or dihydroxyl end-functional PEGs into macroCTAs by introduction of a xanthate moiety, and then used them in RAFT-mediated polymerization of VAc. PEG-b-PVAc diblock copolymer was obtained when the macroCTA had a propionyl ester leaving group (PEG-X1, Scheme 14), whereas under the same experimental conditions the macroCTA with a phenylacetyl ester leaving group (PEG-X2, Scheme 14) inhibited the polymerization.…”

Section: Preparation Of a Macroraft Agent From A Preformed Polymermentioning

confidence: 99%

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RAFT Polymerization of Vinyl Esters: Synthesis and Applications

et al. 2014

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This article is the first comprehensive review on the study and use of vinyl ester monomers in reversible addition fragmentation chain transfer (RAFT) polymerization. It covers all the synthetic aspects associated with the definition of precision polymers comprising poly(vinyl ester) building blocks, such as the choice of RAFT agent and reaction conditions in order to progress from simple to complex macromolecular architectures. Although vinyl acetate was by far the most studied monomer of the range, many vinyl esters have been considered in order to tune various polymer properties, in particular, solubility in supercritical carbon dioxide (scCO 2 ). A special emphasis is given to novel poly(vinyl alkylate)s with enhanced solubilities in scCO 2 , with applications as reactive stabilizers for dispersion polymerization and macromolecular surfactants for CO 2 media. Other miscellaneous uses of poly(vinyl ester)s synthesized by RAFT, for instance as a means to produce poly(vinyl alcohol) with controlled characteristics for use in the biomedical area, are also covered.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Preparation Of a Macroraft Agent From A Preformed Polymermentioning

confidence: 99%

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RAFT Polymerization of Vinyl Esters: Synthesis and Applications

et al. 2014

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“…[55] For many of these systems so-called selective initialization was observed in which there is substantial conversion of the initial RAFT agent into a single unit species before conversion into higher molecular weight chains.The effect is attributed to the rate constant of addition of the 'R' radical to MA being substantially slower than that for propagation. [56] The course of the RAFT polymerization of butyl acrylate (BA) and St with cumyl (22) and cyanoisopropyl dithiobenzoate (24) was followed by electron spin resonance (ESR) spectroscopy.…”

Section: Mechanism Of Raftmentioning

confidence: 99%

“…C Compounds not used as RAFT agents directly but served as precursors to other RAFT agents. (VAc) [55] NVP [55,379] 366 [380] NVPI [220] 367 [380] 368 [380] O S S 209 210* [283,381] O S S NVC [283,382,383] NVCL [384] NVP [381] NVPI [220] 366 [380] 367 [380] 368 [380] (VAc) [55] (NVP) [55] NVC-b-310 [382] NVC-b-311 [382] NVP-b-VAc [381] O S S O OH 211* [385] 212 [386] BA [387] (DEGMA) [386] EHA [387] St [72] VAc [388] (BA-b-AA) [386] VAc [55,385] NVP [55] (DEGMA-b-AA) [386] 213* [283] …”

Section: S S S O Hn Possmentioning

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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Synthesis of N‐Vinyl Lactam Copolymers by Controlled Radical Polymerizations

Zheng

Sarkar

et al. 2021

Handbook of Pyrrolidone and Caprolactam Based Materials

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Free radical polymerization is one of the most versatile techniques for commercial and labscale production of high molecular weight polymers. This chapter discusses recent advances made in the synthesis of polyvinyl pyrrolidone or polyvinyl caprolactam and their copolymers with other monomers using Controlled Radical Polymerization (CRP) techniques like Nitroxide Mediated Polymerization (NMP), Atom Transfer Radical Polymerization (ATRP), Organometallic‐Mediated Radical Polymerization, and Reversible Addition Fragmentation Chain‐Transfer (RAFT) Polymerization. In NMP, nitroxides or alkoxyamines are used to direct the reactions to achieve polymerization control. ATRP is among the most effective and widely used methods of CRP. Controlled polymerization of unconjugated monomers is inherently difficult with both ATRP and NMP. RAFT utilizes a chain transfer agent to control the molecular weight and polydispersity of the resultant polymer by reversible addition and fragmentation events with the endcapped polymer containing the RAFT agent.

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In-Situ NMR Spectroscopy for Probing the Efficiency of RAFT/MADIX Agents

Cited by 92 publications

References 9 publications

RAFT Polymerization of Vinyl Esters: Synthesis and Applications

RAFT Polymerization of Vinyl Esters: Synthesis and Applications

Living Radical Polymerization by the RAFT Process - A Second Update

Synthesis of N‐Vinyl Lactam Copolymers by Controlled Radical Polymerizations

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