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Living cationic polymerization is a living polymerization technique involving cationic propagating species.〔''Controlled and living polymerizations: methods and materials'' 2009 Krzysztof Matyjaszewski,Axel H. E. Muller〕 It enables the synthesis of very well defined polymers (low molar mass distribution) and of polymers with unusual architecture such as star polymers and block copolymers and living cationic polymerization is therefore as such of commercial and academic interest. ==Basics== The basic reaction steps are: iodine. In carbocationic polymerization the active site is a carbocation with a counterion in close proximity. : A+B− + H2C=CHR → A-CH2-RHC+----B− * Chain propagation: : A-CH2-RHC+----B− + H2C=CHR → A-(CH2-RHC)n-CH2-RHC+----B− * Chain termination: : A-(CH2-RHC)n-CH2-RHC+----B− → A-(CH2-RHC)n-CH2-RHC-B * chain transfer: : A-(CH2-RHC)n-CH2-RHC+----B− → A-(CH2-RHC)n-CH2=CR H+B− Living cationic polymerization is characterised by defined and controlled initiation and propagation while minimizing side-reactions termination and chain transfer. Transfer and termination do occur but in ideal living systems the active ionic propagating species are in chemical equilibrium with the dormant covalent species with an exchange rate much faster than the propagation rate. Solution methods require rigorous purification of monomer and solvent although conditions are not as strict as in anionic polymerization. Common monomers are vinyl ethers, alpha-methyl vinyl ethers, isobutene, styrene, methylstyrene and N-vinylcarbazole. The monomer is nucleophilic and substituents should be able to stabilize a positive carbocationic charge. For example para-methoxystyrene is more reactive than styrene itself. Initiation takes place by an initiation/coinitiation binary system, for example an alcohol and a Lewis acid. The active electrophile is then a proton and the counter ion the remaining alkoxide which is stabilized by the Lewis acid. With organic acetates such as cumyl acetate the initiating species is the carbocation R+ and the counterion is the acetate anion. In the iodine/HI system the electrophile is again a proton and the carbocation is stabilized by the triiodide ion. Polymerizations with Diethylaluminium chloride rely on trace amounts of water. A proton is then accompanied by the counterion Et2AlClOH−. With tert-butyl chloride Et2AlCl abstracts a chlorine atom to form the tert-butyl carbocation as the electrophile. Efficient initiators that resemble the monomer are called cationogens. Termination and chain transfer are minimized when the initiator counterion is both non-nucleophilic and non-basic. More polar solvents promote ion dissociation and hence increase molar mass. Common additives are electron donors, salts and proton traps . Electron donors (e.g. nucleophiles, Lewis bases) for example dimethylsulfide and dimethylsulfoxide are believed to stabilize the carbocation. The addition of salt for example a tetraalkylammonium salt, prevents dissociation of the ion pair that is the propagating reactive site. Ion dissociation into free ions lead to non-living polymerization. Proton traps scavenge protons originating from protic impurities. 抄文引用元・出典: フリー百科事典『 ウィキペディア（Wikipedia）』 ■ウィキペディアで「living cationic polymerization」の詳細全文を読む スポンサード リンク
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