title: Synthesis of structurally well-defined telechelic polymers by organostibine-mediated living radical polymerization: in situ generation of functionalized chain-transfer agents and selective omega-end-group transformations.
abstract: Several organostibine chain-transfer agents possessing polar functional groups have been prepared by the reactions of azo initiators and tetramethyldistibine (1). Carbon-centered radicals thermally generated from the azo initiators were trapped by 1 to yield the corresponding organostibine chain-transfer agents. The high yields observed in the synthesis of the chain-transfer agents strongly suggest that distibines have excellent radicophilic reactivity. As the reactions proceeded under neutral conditions, functional groups that are incompatible with ionic conditions were incorporated into the chain-transfer agents. The chain-transfer agents were used in living radical polymerization to synthesize the corresponding alpha-functionalized polymers. As the functional groups in the chain-transfer agents did not interfere with the polymerization reaction, well-controlled polymers possessing number-average molecular weights (M(n)s) predetermined by the monomer/transfer agent ratios were synthesized with low polydispersity indices (PDIs). The organostibanyl omega-polymer ends were transformed into a number of different functional groups by radical-coupling, radical-addition, and oxidation reactions. Therefore, it was possible to synthesize well-controlled telechelic polymers with the same and also with different functional groups at their alpha- and omega-polymer ends. Distibine 1 was also found to increase PDI control in the living radical polymerization of styrene and methyl methacrylate (MMA) using a purified organostibine chain-transfer agent. Well-controlled poly(methyl methacrylate)s with M(n) values ranging from 10 000 to 120 000 with low PDIs (1.05-1.15) were synthesized by the addition of a catalytic amount of 1. The results have been attributed to the high reactivity of distibine 1 towards polymer-end radicals, which are spontaneously deactivated to yield organostibine dormant species.
authors.affiliation: Institute for Chemical Research, Kyoto University, Uji, Kyoto, Japan. yamago@scl.kyoto-u.ac.jp
authors.forename: Shigeru
authors.initials: S
authors.lastname: Yamago
authors.forename: Takeshi
authors.initials: T
authors.lastname: Yamada
authors.forename: Manabu
authors.initials: M
authors.lastname: Togai
authors.forename: Yuu
authors.initials: Y
authors.lastname: Ukai
authors.forename: Eiichi
authors.initials: E
authors.lastname: Kayahara
authors.forename: Na
authors.initials: N
authors.lastname: Pan