Anionic polymerization of 1,3‐cyclohexadiene: Addition of poly(1,3‐cyclohexadienyl)lithium to fullerene‐C60

The addition of poly(1,3‐cyclohexadiene) (PCHD) carbanion to fullerene‐C₆₀ (C₆₀) was examined using poly(1,3‐cyclohexadienyl)lithium (PCHDLi), PCHDLi/1,4‐diazabicyclo2,2,2]octane (DABCO), and PCHDLi/N,N,N′,N′‐tetramethylethylenediamine (TMEDA). The reactivity of PCHD carbanions was in the order of PCHDLi > PCHDLi/DABCO > PCHDLi/TMEDA, regardless of the polymer main chain structure. PCHDLi, PCHDLi/DABCO, and PCHDLi/TMEDA in toluene formed σ‐structures, σ‐ and π‐structures, and π‐structures, respectively. The degree of localization on the terminal carbanion was a main factor for control of this addition reaction. In addition, all 1,2‐cyclohexadiene (1,2‐CHD) unit sequences contributed to preventing the addition reaction. That is, large steric hindrance of the polymer main chain was another important factor to control the addition reaction. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010