Advances in RAFT polymerization: the synthesis of polymers with defined end-groups

Moad, Graeme; Chong, Y. K.; Postma, Almar; Rizzardo, Ezio; Thang, San H.

doi:10.1016/j.polymer.2004.12.061

Cited by 753 publications

(803 citation statements)

References 75 publications

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“…TERP includes thermal dissociation and degenerative chain transfer (DT) as control mechanisms, in which the main control mechanism is DT, and has a sufficiently high chain transfer constant (C ex ), which is important for good control/livingness in DT. In a reversible addition-fragmentation chain transfer polymerization, which is a well-known CLRP based on the same DT mechanism, an intermediate radical was formed, [4][5][6] resulting in fewer choices of macroinitiators for the preparation of block copolymers. Because organotellurium compounds operating as control agents in TERP do not form the intermediate radical and types of monomers such as methacrylate, acrylate, styrene, acrylamides, and even non-conjugated monomers can be polymerized by TERP, TERP has a high potential for the precision synthesis of functional polymers.…”

Section: Introductionmentioning

confidence: 99%

Effect of stirring rate on particle formation in emulsifier-free, organotellurium-mediated living radical emulsion polymerization (emulsion TERP) of styrene

Moribe

Kitayama

Suzuki

et al. 2011

Polym J

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Particle formation during the initial stages of emulsifier-free organotellurium-mediated living radical emulsion polymerization (emulsion TERP) of styrene at 601C was investigated at two stirring rates (220 and 1000 r.p.m.), in which the styrene phase floated as a layer on an aqueous phase at 220 r.p.m. or became dispersed as droplets at 1000 r.p.m. A water-soluble TERP agent, poly(methacrylic acid) (PMAA)-methyltellanyl (PMAA 30 -TeMe) and a water-soluble thermal initiator, 4,4¢-azobis(4-cyanovaleric acid), at alkaline pH were used. The control/livingness was better at 1000 r.p.m. than at 220 r.p.m., and the particle size distribution was also affected by the stirring rate: both nanometer-sized and submicrometer-sized particles were observed at 220 r.p.m., and mainly nanometer-sized particles were observed at 1000 r.p.m. Because the percentage of PMAA 30 -TeMe consumed in the initial stage was much higher at 1000 r.p.m. than at 220 r.p.m., self-assembly nucleation preferentially occurred at 1000 r.p.m., resulting in nanometer-sized particles and good control/livingness. Stirring at 1000 r.p.m. only in the initial stage of the emulsion TERP followed by 220 r.p.m. induced good control/livingness and the formation of mainly nanometer-sized particles. It is concluded that a high stirring rate in the initial stage is important for the emulsion TERP of styrene to obtain good control/ livingness and to control the particle formation mechanism.

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Section: Introductionmentioning

confidence: 99%

Effect of stirring rate on particle formation in emulsifier-free, organotellurium-mediated living radical emulsion polymerization (emulsion TERP) of styrene

Moribe

Kitayama

Suzuki

et al. 2011

Polym J

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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%

“…[23,24] However these processes, while they result in loss of the thiocarbonylthio group, leave reactive end group functionality and thus are not suitable in many circumstances. Thermolysis [5,8,25,26] and various radical-induced reactions (reduction, [5,8,[27][28][29] termination [5,30] ) provide solutions to this dilemma and can provide desulfurization by complete end-group elimination/transfer.…”

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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“…20 Bis(dodecylsulfanylthiocarbonyl) disulfide (2.92 g, 0.0053 mol) and ACP (2.00 g, 0.0079 mol) in ethyl acetate (100 mL) were heated under reflux for 24 h. After removing of the volatiles under vacuum, the crude product was washed with water and purified by column chromatography using hexane/ethyl acetate ¼ 5:5 (v/v) as the eluent. The product was orange color oil (2.04 g, 48% yield).…”

Section: Characterizationsmentioning

confidence: 99%

One‐step synthesis of block copolymers using a hydroxyl‐functionalized trithiocarbonate RAFT agent as a dual initiator for RAFT polymerization and ROP

Kang

Shin

et al. 2012

J. Polym. Sci. A Polym. Chem.

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A range of well-defined block copolymers were synthesized using 4-cyano-4-(dodecylsulfanylthiocarbonyl)sulfanylpentanol (CDP) as a dual initiator for reversible additionfragmentation chain transfer (RAFT) polymerization and ring-opening polymerization (ROP) in a one-step process. Styrene, (meth)acrylate, and acrylamide monomers were polymerized in a controlled manner for one block composed of vinyl monomers, and d-valerolactone (VL), e-caprolactone (CL), trimethylene carbonate (TMC), and L-lactide (LA) were used for the other block composed of cyclic monomers. Diphenyl phosphate was used as a catalyst for the ROP of VL, CL, and TMC, and 4-dimethyamino pyridine for the ROP of LA. These catalysts did not interfere with RAFT polymerization and the synthesis of various block copolymers proceeded in a controlled manner. CDP was found to be a very useful dual initiator for a one-step synthesis of various block copolymers by a combination of RAFT polymerization and ROP. V C 2012 Wiley Periodicals, Inc. J.

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Advances in RAFT polymerization: the synthesis of polymers with defined end-groups

Cited by 753 publications

References 75 publications

Effect of stirring rate on particle formation in emulsifier-free, organotellurium-mediated living radical emulsion polymerization (emulsion TERP) of styrene

Effect of stirring rate on particle formation in emulsifier-free, organotellurium-mediated living radical emulsion polymerization (emulsion TERP) of styrene

Thermolysis of RAFT-Synthesized Poly(Methyl Methacrylate)

One‐step synthesis of block copolymers using a hydroxyl‐functionalized trithiocarbonate RAFT agent as a dual initiator for RAFT polymerization and ROP

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