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Anionic Polymerization Chemistry of Epoxides: Electron‐Transfer Processes
Author(s) -
Quirk Roderic P.,
Pickel Deanna L.,
Hasegawa Hiroaki
Publication year - 2005
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/masy.200550807
Subject(s) - regioselectivity , chemistry , styrene oxide , surface modification , polymer chemistry , dimer , electron transfer , polymerization , styrene , adduct , methylene , photochemistry , reaction mechanism , polymer , anionic addition polymerization , organic chemistry , copolymer , catalysis
Abstract The reaction of poly(styryl)lithium (PSLi) with styrene oxide (SO) in benzene solution has been investigated. In addition to the functionalized polymer (83.5 wt %) the product mixture consisted of unfunctionalized polymer (9 wt %) and a dimeric product (5.6 wt %). The structure of the dimeric product was determined to be the head‐to‐head dimer. The regiochemistry of the addition reaction was unselective: 53 mol % addition to the methylene carbon and 47 mol % corresponding to addition to the hindered, methine carbon. Based on the formation of the dimer and the lack of regioselectivity, a pathway involving electron transfer from PSLi to SO was proposed. To further investigate the propensity to react via this electron‐transfer mechanism, the SO functionalization of the adduct of PSLi with 1,1‐diphenylethylene was investigated as well as the functionalization of PSLi with 1,1‐diphenylethylene oxide.