Anionic Polymerization of 1,3-Cyclohexadiene: Reactivity of Poly(1,3-cyclohexadienyl)lithium

• Published in: Macromolecular chemistry and physics Vol. 207; no. 23; pp. 2215 - 2221
• Main Author: Natori, Itaru
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.12.2006; WILEY‐VCH Verlag; Wiley
• Subjects: 1,3‐cyclohexadiene; 3-cyclohexadiene; 3-cyclohexadienyl)lithium; anionic polymerization; Applied sciences; Exact sciences and technology; living polymerization; Organic polymers; Physicochemistry of polymers; poly; poly(1,3‐cyclohexadienyl)lithium; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; reactivity; reactivity; Living polymer; Bromocarbon; Experimental study; Solution polymerization; Cyclodiene polymer; Lithium Organic compounds; 1,3-cyclohexadiene; living polymerization; Anionic polymerization; Chemical reactivity; Nucleophilic substitution; Fluorene derivatives; Nucleophilicity; poly(1,3-cyclohexadienyl)lithium
• ISSN: 1022-1352; 1521-3935
• DOI: 10.1002/macp.200600371

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 CLi bonds in PCHDLi. Post‐polymerization reaction of poly(1,3‐cyclohexadienyl)lithium (PCHDLi) and 9‐bromofluorene (9‐BFL).