Benzyl and Cumyl Dithiocarbamates as Chain Transfer Agents in the RAFT Polymerization of <i>N</i>-Isopropylacrylamide. In Situ FT-NIR and MALDI−TOF MS Investigation

Schilli, Christine; Lanzendörfer, Michael G.; Müller, Axel H. E.

doi:10.1021/ma0121159

Cited by 347 publications

(344 citation statements)

References 17 publications

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“…Systems studied by mass spectrometry include (polymer/ RAFT agents): PNIPAM/20,22, [78] PNIPAM/39,40, [93] PVAc/49, [48] PS/21, [126] PS/69, [106] PMMA/8,11, [100] PBA/ 57,63, [127] PMA/21,22,24, [81,83] PEA/79, [49] and poly-(acenaphthalene)/81. [128] ESI is a softer ionization technique than MALDI-TOF and is more likely to leave the end groups intact to be observed in the mass spectrum.…”

Section: Evidence In Support Of the Raft Mechanismmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process

Moad¹,

Rizzardo²,

Thang³

2005

Aust. J. Chem.

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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Section: Evidence In Support Of the Raft Mechanismmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process

Moad¹,

Rizzardo²,

Thang³

2005

Aust. J. Chem.

2,134

1,894

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“…42 Similar to N-vinylcarbazole, N-vinylimidazolium salt can be regarded as a non-conjugated N-vinyl monomer. In contrast, dithiocarbamate-type CTAs in which the lone pair on the nitrogen atom is part of the aromatic pyrrole ring system, have been employed for the RAFT polymerization of conventional conjugated monomers such as styrene, 43,44 methyl acrylate 44 and N-isopropylacrylamide, 45 and have been used to polymerize less active monomers such as N-vinylphthalimide 46 and N-vinylnaphthalimide. 47 On the basis of the aforementioned results, we evaluated two R-designed tetrafunctional CTAs, including a CTA 1 and a CTA 2, as shown in Scheme 1.…”

Section: Synthesis Of Poly(n-vinylimidazolium Salt) Starsmentioning

confidence: 99%

Temperature-responsive self-assembly of star block copolymers with poly(ionic liquid) segments

Mori

Ebina

Kambara

et al. 2012

Polym J

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Novel star block copolymers containing poly(N-vinylimidazolium salt) as a poly(ionic liquid) segment and poly(N-isopropylacrylamide) (poly(NIPAAm)) as a thermoresponsive segment were synthesized by reversible additionfragmentation chain transfer (RAFT) polymerization. Two R-designed tetrafunctional chain transfer agents (CTAs), including a xanthate-type CTA and a dithiocarbamate-type CTA, were compared for the polymerization of 1-ethyl-3-vinylimidazolium bromide (VEI-Br), which is an ionic liquid-type monomer. The dithiocarbamate-type tetrafunctional CTA was the most efficient CTA for the controlled synthesis of four-armed poly(VEI-Br) stars with low polydispersity values and controlled molecular weights. Star block copolymers with inner thermoresponsive segments connected to their core were synthesized by the RAFT polymerization of VEI-Br, using poly(NIPAAm) stars. In contrast, the RAFT polymerization of NIPAAm using poly(VEI-Br) stars afforded star block copolymers, with block arms consisting of outer block copolymer segments of thermoresponsive poly(NIPAAm). Thermally induced phase separation behavior and assembled structures of star block copolymers were studied in aqueous solution. Keywords: block copolymer; micelle; poly(ionic liquid); self-assembly; star polymer; star block copolymer; thermoresponsive polymer INTRODUCTION Recently, considerable attention has been paid to polymerized ionic liquids or polymeric ionic liquids, which are macromolecules obtained from the polymerization of ionic liquid monomers. [1][2][3] Polymeric ionic liquids with unique and attractive properties can be obtained by adjusting the structure of the cation (for example, imidazolium, pyridinium and tetraalkylammonium) and the anion (for example, halide, tetrafluoroborate and hexafluorophosphate). Potential applications of polymeric ionic liquids include polymeric electrolytes, catalytic membranes, ionic conductive materials, CO 2 absorbents, microwave absorbents and porous materials. Imidazolium salt is the most popular cation introduced into polymer backbones. A variety of polymers containing imidazolium moieties on their side chains have been developed, including poly(meth)acrylate, 4-7 polystyrene 8,9 and poly(N-vinyl imidazolium) 10-13 derivatives. The majority of these poly(ionic liquid)s were prepared by conventional radical polymerization. In addition to the structure of the substituent on the imidazolium ring, the solubility and properties of poly(Nvinylimidazolium salt) depend on the structure of the counteranion.As a result of recent progress in controlled radical polymerization (also known as controlled or living radical polymerization or reversible deactivation radical polymerization), well-defined block copolymers containing imidazolium moieties have been synthesized. 14,15 For example, Waymouth et al. 16,17 demonstrated the

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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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Benzyl and Cumyl Dithiocarbamates as Chain Transfer Agents in the RAFT Polymerization of N-Isopropylacrylamide. In Situ FT-NIR and MALDI−TOF MS Investigation

Cited by 347 publications

References 17 publications

Living Radical Polymerization by the RAFT Process

Living Radical Polymerization by the RAFT Process

Temperature-responsive self-assembly of star block copolymers with poly(ionic liquid) segments

Thermolysis of RAFT-Synthesized Poly(Methyl Methacrylate)

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