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Anionic Polymerization of 1,3‐Cyclohexadiene: Reactivity of Poly(1,3‐cyclohexadienyl)lithium
Author(s) -
Natori Itaru
Publication year - 2006
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.200600371
Subject(s) - dabco , chemistry , nucleophile , polymerization , reactivity (psychology) , anionic addition polymerization , tetramethylethylenediamine , polymer chemistry , octane , lithium (medication) , steric effects , medicinal chemistry , photochemistry , organic chemistry , catalysis , polymer , medicine , alternative medicine , pathology , endocrinology
Summary: The reactivity of poly(1,3‐cyclohexadienyl)lithium (PCHDLi), as a species for the propagation of the anionic polymerization of 1,3‐cyclohexadiene (1,3‐CHD), was examined using a post‐polymerization reaction of PCHDLi and 9‐bromofluorene (9‐BFL). The degree of nucleophilicity of the PCHDLi systems was determined as PCHDLi/1,4‐diazabicyclo[2,2,2]octane (DABCO) > PCHDLi/ N,N,N′,N′ ‐tetramethylethylenediamine (TMEDA) > PCHDLi. The nucleophilicity of PCHDLi was strengthened by the complexation of TMEDA to Li, and was saturated when the TMEDA/Li molar ratio was over 1.0. The rate of polymerization increased with increasing nucleophilicity of PCHDLi. In addition, the molar ratio of the 1,2‐addition (1,2‐CHD unit)/1,4‐addition (1,4‐CHD unit) seemed to be strongly affected by both the nucleophilicity of PCHDLi and the steric hindrance of CLi bonds in PCHDLi.Post‐polymerization reaction of poly(1,3‐cyclohexadienyl)lithium (PCHDLi) and 9‐bromofluorene (9‐BFL).