Highly Controlled Living Radical Polymerization through Dual Activation of Organobismuthines

Yamago, Shigeru; Kayahara, Eiichi; Kotani, Masahiro; Ray, Biswajit; Kwak, Yungwan; Goto, Atsushi; Fukuda, Takeshi

doi:10.1002/anie.200604473

Cited by 145 publications

(119 citation statements)

References 25 publications

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“…A typical example is the iodide-mediated polymerization (Scheme 2e), where X is iodine. Organotelluriummediated living radical polymerization (TERP: X ¼ MeR) (Scheme 2h) [24], organostibine one (SBRP: X ¼ SbR 2 ) [25], and organobismuthine one (BIRP: X ¼ BiR 2 ) [26] are also based on this mechanism, while interestingly the DC mechanism coexists in TERP and BIRP with the main mechanism being DT in both cases. The cobalt and titanium systems (X ¼ Co and Ti complexes) (Scheme 2d) are also assumed to include the two mechanisms.…”

Section: Degenerative Chain Transfer (Dt) Mechanismmentioning

confidence: 99%

“…Such an experiment was carried out for the nitroxide (Scheme 2b) [27], iodide (e) [28], ATRP (f) [29], RAFT (g) [30], TERP (h) [31], SBRP (h) [25,32], and BIRP (h) [26] systems. The established mechanisms are summarized in Scheme 4, as the classification was mentioned in the above sections.…”

Section: Experimental Establishment Of Activation Mechanism For Indivmentioning

confidence: 99%

“…Examples are listed in Scheme 2. They include sulfur compounds (Scheme 2a [9] and g [10]), stable nitroxides (b) [11][12][13], stable nitrogen and carbon compounds (c) [14][15][16][17], transition metal complexes (d) [18,19], iodine (e) [20], halogens with transition metal catalysts (f) [21][22][23], and tellurium, stibine, and bismuth compounds (h) [24][25][26].…”

Section: Examples Of Capping Agent Xmentioning

confidence: 99%

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Reversible chain transfer catalyzed polymerization (RTCP): A new class of living radical polymerization

Goto

Tsujii

Fukuda

2008

Polymer

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a b s t r a c tThis article introduces the new family of living radical polymerizations with germanium (Ge), tin (Sn), phosphorus (P), and nitrogen (N) catalysts which we recently developed. The polymerizations are based on a new reversible activation mechanism, Reversible chain Transfer (RT) catalysis. Low-polydispersity polymers are obtained in the homopolymerizations and random and block copolymerizations of styrene, methyl methacrylate, and functional methacrylates. The background, performance, and kinetic features of the polymerizations are described. Attractive features of the catalysts include their high reactivity, low toxicity (Ge, P, and N), low cost (P and N), and ease of handling (robustness).

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Section: Degenerative Chain Transfer (Dt) Mechanismmentioning

confidence: 99%

Section: Experimental Establishment Of Activation Mechanism For Indivmentioning

confidence: 99%

Section: Examples Of Capping Agent Xmentioning

confidence: 99%

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Reversible chain transfer catalyzed polymerization (RTCP): A new class of living radical polymerization

Goto

Tsujii

Fukuda

2008

Polymer

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“…These systems include atom transfer radical polymerization (ATRP), [3][4][5][6][7] stable free radical polymerization (nitroxide-mediated polymerization (NMP) [8][9][10] and organometallic radical polymerization (OMRP), [11][12][13][14][15] and degenerative transfer polymerization (with reversible addition-fragmentation chain transfer (RAFT)) [16][17][18][19] polymerization being the most extensively studied, as well as polymerizations performed in the presence of iodine, [20] organostibine, -tellurium, and -bismuthine compounds (SBRP/TERP/BIRP)]. [21][22][23] Poly(N-vinylcarbazole) (PNVK) is one of the extensively studied photoconductive polymers; with potential applications as polymeric light emitting diodes, organic photorefractive materials, and photovoltaic devices. Since the first successful use of PVNK in electrophotographic applications, [24,25] polymers with carbazole moieties have been often studied.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of poly(N-vinyl carbazole)-based block copolymers by sequential polymerizations of RAFT–ATRP

Huang

Hsieh

Hsu

et al. 2014

Polymer

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“…2 Indeed different types of CRP techniques have been reported which facilitated the synthesis of broad variety of polymeric materials with predetermined molecular weight, narrow MWD and desired chain end groups. CRP was achieved through iniferter (initiation transfer termination), 3 stable nitroxide radicals, 4 triazolinyl radicals, 5 organo-bismuthine, 6 organotellurium, 7 organo-cobalt, 8 organo-stilbene, 9 alkyl-9-BBN, 10 reversible addition-fragmentation-chain transfer (RAFT), 11 degenerative chain transfer by alkyl iodide, 12 and atom transfer radical polymerization (ATRP). 13,14 All the CRP methods include activation and deactivation steps with their respective rate constants, k act and k deact respectively and k deact is higher in all the cases to get controlled radical polymerization of monomers.…”

mentioning

confidence: 99%

Novel Telechelic 2-Methyl-2-Bromopropionate Terminated Polyurethane Macroinitiator for the Synthesis of ABA type Tri-block Copolymers through Atom Transfer Radical Polymerization of Methyl Methacrylate

Verma

Kannan

2008

Polym J

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Novel telechelic 2-methyl-2-bromopropionate terminated polyurethane macroinitiator was synthesized and used further to polymerize methyl methacrylate to yield poly(methyl methacrylate)-block-polyurethane-block-poly(methyl methacrylate) triblock copolymers through atom transfer radical polymerization. Number-average molecular weight (M n ) was increased linearly with increasing polymerization time and conversion. Molecular weight distribution becomes narrower as the polymerization time increases and theoretical M n values of the tri-block copolymers were comparable to the experimental M n values. Structures of the macroinitiator and the tri-block copolymers were confirmed by 1 H NMR, 13 C NMR and FT-IR spectroscopic techniques. Mole percentage of poly(methyl methacrylate) in the triblock copolymers was calculated using 1 H NMR spectroscopy and was found to be comparable with the gel permeation chromatography results. Presence of two phases in the tri-block copolymers has been confirmed through differential scanning calorimetric studies.KEY WORDS: ATRP / Block Copolymers / Poly(methyl methacrylate) / Polyurethanes / Living anionic polymerization was first discovered by Szwarc, 1 where polymer chain propagation took place without chain breaking reactions such as chain transfer and chain termination. As a result polymers with defined molecular weight, narrow molecular weight distribution (MWD) and desired end groups were achieved through this method. But it requires stringent experimental conditions and highly pure monomers and solvents. On contrary, free radical polymerization is used widely to polymerize more than 70% of vinyl and acrylate monomers in industries but it has poor control over degree of polymerization, MWD and end functionalization during polymerization. In recent years, the idea of introducing livingness in free radical polymerization was proposed and it was termed as controlled radical polymerization (CRP).2 As the conversion increases M n also should increase linearly in any living polymerizations.2 In conventional radical polymerization there is no linear increase of molecular weight with the conversion.2 Hence in all CRP routes linear increase of molecular weight with conversion should takes place to show that they are following living polymerization mechanism.

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Highly Controlled Living Radical Polymerization through Dual Activation of Organobismuthines

Cited by 145 publications

References 25 publications

Reversible chain transfer catalyzed polymerization (RTCP): A new class of living radical polymerization

Reversible chain transfer catalyzed polymerization (RTCP): A new class of living radical polymerization

Synthesis of poly(N-vinyl carbazole)-based block copolymers by sequential polymerizations of RAFT–ATRP

Novel Telechelic 2-Methyl-2-Bromopropionate Terminated Polyurethane Macroinitiator for the Synthesis of ABA type Tri-block Copolymers through Atom Transfer Radical Polymerization of Methyl Methacrylate

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