Stereospecific Living Radical Polymerization

Kamigaito, Masami; Satoh, Kotaro

doi:10.1295/kobunshi.55.250

Cited by 2 publications

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“…38,[40][41][42] As for the metal-catalyzed living radical polymerization, we first examined the combination of the dinuclear iron(I) complex [Fe 2 Cp 2 (CO) 4 ] and lanthanide triflate (for example, Y(OTf) 3 and Yb(OTf) 3 ) to control the molecular weight and the tacticity, respectively, in the radical polymerization of acrylamide derivatives (Figure 15). 115 The low oxidation state iron(I) complex, which is one of the most active and versatile metal catalysts, induced an efficient and rather faster polymerization of N,N-dimethylacrylamide (DMAM) in the presence of Y(OTf) 3 than in its absence.…”

Section: Stereospecific Living Radical Polymerizationmentioning

confidence: 99%

“…Another further control of radical polymerization is the dual control of the polymer molecular weight and tacticity, which have not yet been fully attained. 38,[40][41][42] This review covers recent developments in metal-catalyzed living radical polymerization, focusing on our research studies, including the metal-catalytic system, the precision synthesis of well-controlled polymers, and the simultaneous control of the molecular weight and tacticity using metal-catalyzed stereospecific living radical polymerizations. Although there has been great progress in other…”

Section: Introductionmentioning

confidence: 99%

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Recent developments in metal-catalyzed living radical polymerization

Kamigaito

2010

Polym J

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This review presents a short overview of recent developments in metal-catalyzed living radical polymerization, mainly focusing on our recent research studies related to the subject. Metal-catalyzed living radical polymerization or atom transfer radical polymerization, which was originally developed via evolution of the metal-catalyzed Kharasch or atom transfer radical addition to chain-growth polymerization via reversible activation, has now been widely developed in many aspects. The effective metal catalysts include various transition metals, such as ruthenium, copper, iron and nickel, and highly active and versatile catalytic systems have been developed by designing ligands, applying lower oxidation metal species and using additives to widen the scope of controllable monomers and to minimize the amount of metal catalysts and the residual metals in the products. The development of the initiating systems has enabled the synthesis of a wide variety of novel, well-defined polymers, including end-functionalized, block, graft and star polymers, but also more complicated polymers possessing multiple controlled structures. Furthermore, metal-catalyzed living radical polymerization has been judiciously combined with stereospecific radical polymerization based on the use of polar solvents or Lewis acid additives, resulting in the dual control of the molecular weight and the tacticity of the resulting polymers and enabling the preparation of stereoblock and stereogradient polymers. Keywords: block polymer; living radical polymerization; precision polymer synthesis; transition metal catalyst; star polymer; stereospecific polymerization INTRODUCTIONSince the discovery of metal-catalyzed living radical polymerization or atom transfer radical polymerization (ATRP), there have been many developments in this research area, including active and versatile metal catalytic systems; the scope of controllable monomers; well-defined polymers with various controlled architectures; hybridization of the controlled polymers with inorganic, metal and biomolecular compounds; and attempts or real applications to a variety of industrial materials. 1-17 Besides these metal catalytic systems, there have also been substantial developments in various living radical polymerizations, such as nitroxide-mediated polymerizations, reversible addition fragmentation chain-transfer polymerizations and others, and in all of these, there are characteristic features of the mechanisms and components. [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] The metal-catalyzed living radical polymerization was originally discovered via evolution of the metal-catalyzed Kharasch or atom transfer radical addition reaction 35 to the chain-growth polymerization of vinyl monomers (Figure 1). 1 The initiating system generally consists of a transition metal complex in a lower oxidation state and an organic halide, in which the carbon-halogen bond of the halogen compound is activated by the metal catalyst to generate the carbon radical species upon a one-e...

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