A Convenient, High Yielding Cleavage of the Thiocarbonyl Group in Xanthates

Quiclet‐Sire, Béatrice; Zard, Samir Z.

doi:10.5012/bkcs.2010.31.03.543

Cited by 23 publications

(20 citation statements)

References 25 publications

(2 reference statements)

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“…RAFT-synthesized polymers with xanthate end-groups react with ozone quantitatively to form the corresponding polymer with a thiolocarbonate end-group. [606,607] The mechanism was not fully elucidated but the thiocarbonyl is replaced with a carbonyl and sulfuric acid is formed as a by-product (Scheme 10). The process was claimed to also be applicable to other RAFT end-groups (trithiocarbonates, dithioesters) and a patent was filed on the use of this process.…”

Section: Oxidationmentioning

confidence: 99%

“…[44] The first reports involved the use of N,N-dialkyl dithiocarbamate derivatives as ATRP initiators. Dithiocarbamates do not provide effective control over the polymerization [241] MMA, St 456 Propylamine Network cleavage [603] BA, St 441 Butylamine/TCEP/BA In situ thiol-ene multiblock cleavage [604] PEGA 47 Butylamine/TCEP/divinyl sulfone In situ thiol-ene [281] MA, DMAm, NIPAm, St, C 2 H 5 S (121) Hydrazine - [375] St, PEGMA Ph (54, 18) Hydrazine - [375] St Ph (18) Hydrazine Used in thiol-epoxide [193] St Ph (18) DEAm (18) Hydrazine In situ thiol-epoxide [193] St/AcS Ph (11) Hydrazine Au nanoparticles [176] EGDMA, 421, 420 Ph (18) Hexylamine Used in thiol-ene or other reaction [588] St PhCH 2 S 1) KOH, 2) Zn/AcOH Au nanoparticles [338] St PhCH 2 S (89) Ethylene diamine Initiator for ROP C [339] HPMAm Ph (11) NaBH 4 /PBu 3 In situ thiol-ene (AA) [161] HPMAm Ph (68) Butylamine MeOH/degassed used in thiol-ene [307] NIPAm Ph (18) NaBH 4 Used in thiol-ene [247] MMA Ph (18) Hexylamine In situ thiol-ene [220] HPMAm Ph (18) Hexylamine In situ thiol-ene [220] NIPAm CH 2 (CO 2 H)CH 2 S (179) Hexylamine In situ thiol-ene [220] NIPAm C 4 H 9 S (159) Hexylamine/DMPP Used in thiol-ene [446] NIPAm C 12 H 25 S (123) Hexylamine/Bu 3 Ph Used in thiol-ene [398] Am Ph (18) NaBH 4 Used in thiol ene [244] DEAm Ph ( StMe OEt Ozone --(C¼O)SOEt [606] BA OEt Ozone --(C¼O)SOEt [607] iBoA 2-pyridyl Air AIBN, THF/Ph 3 P -OH [605] MMA, acrylates Ph Air AIBN, THF/Ph 3 P -OH [182,605] St, acrylates P n S Air AIBN, THF/Ph 3 P -OH [182] MA, BA CH 2 Ph Air AIBN, THF/Ph 3 P -OH [182] St CH 2 Ph Air AIBN, THF/Ph 3 P -OH …”

Section: Atrp-raftmentioning

confidence: 99%

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Living Radical Polymerization by the RAFT Process – A Third Update

2012

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This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(¼S)SR) by a mechanism of reversible addition-fragmentation chain transfer ( Chem. 2009Chem. , 62, 1402. This review cites over 700 publications that appeared during the period mid 2009 to early 2012 covering various aspects of RAFT polymerization which include reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses, and a diverse range of applications. This period has witnessed further significant developments, particularly in the areas of novel RAFT agents, techniques for end-group transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

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Section: Oxidationmentioning

confidence: 99%

Section: Atrp-raftmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process – A Third Update

2012

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“…The ozone molecule can be considered a 1,3‐dipolar compound and is known to present a high reactivity toward olefinic derivatives . Its reactivity on the CS bound is similar to the one observed on the CC . This also means that such a reagent oxidizes the unreacted monomer in the latex, which is interesting for industrial purposes where the reached concentration of residual monomer must be as low as possible.…”

Section: Resultsmentioning

confidence: 99%

“…The process consists of the oxidation of the thiocarbonyl CS function of xanthates to CO using ozone . Ozone is an attractive reagent as it is a hydrophobic gas that easily diffuses into the particles far more rapidly than conventional liquid organic reagents.…”

Section: Resultsmentioning

confidence: 99%

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Selective and Quantitative Oxidation of Xanthate End-Groups of RAFT Poly(n-butyl acrylate) Latexes by Ozonolysis

Matioszek

Dufils

Vinas

et al. 2015

Macromol. Rapid Commun.

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Although various successful strategies have been reported in the past for the postpolymerization modification of the reversible addition‐fragmentation chain transfer (RAFT) terminal group in homogeneous media, no solution is proposed for the tedious case of aqueous polymer dispersions where most of the thiocarbonylthio terminal group is buried into the core of the polymer particle. In this work, ozone is proposed to tackle this important academic and industrial challenge. After preliminary model ozonolysis reactions performed on a xanthate RAFT agent and a derived low molar mass poly(n‐butyl acrylate) (PBA) in dichloromethane solution, it is shown that the hydrophobic nature and strong oxidant properties of ozone are responsible for its efficient diffusion in aqueous PBA latex particles obtained by RAFT and selective and complete transformation of the xanthate terminal group into a thiocarbonate end‐group. In addition to the beneficial total discoloration of the final product, this chemical treatment does not generate any volatile organic compound and leaves the colloidal stability of the polymer particles unaffected, provided that a PBA latex with a sufficiently high Mn of 5000 g mol−1 is selected.

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Reversible Deactivation Radical Polymerization: RAFT

Moad

2022

Macromolecular Engineering

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RAFT polymerization is a form of reversible deactivation radical polymerization (RDRP), which with appropriate attention to reagents and reaction conditions can possess the attributes usually associated with living polymerization (molar mass control, low molar mass dispersity ( Đ ), high end‐group fidelity, capacity for continued chain growth, and access to complex architectures). This article provides an overview of the RAFT mechanism and guidelines for selection of conditions for RAFT polymerization (including selection of monomers, RAFT agents, and initiation processes) for the synthesis of blocks, stars, and networks. Finally, we provide details of methods for RAFT end‐group transformation/removal.

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A Convenient, High Yielding Cleavage of the Thiocarbonyl Group in Xanthates

Abstract: International audienc

Cited by 23 publications

References 25 publications

Living Radical Polymerization by the RAFT Process – A Third Update

Living Radical Polymerization by the RAFT Process – A Third Update

Selective and Quantitative Oxidation of Xanthate End-Groups of RAFT Poly(n-butyl acrylate) Latexes by Ozonolysis

Reversible Deactivation Radical Polymerization: RAFT

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