Chemical modification via lithiation of polymers prepared from acenaphthylene: Comparisons with lithiations of polystyrene

Homo- and co-polymers prepared from acenaphthylene and styrene have been lithiated using butyllithium in the presence of either tetramethylethylenediamine (TMEDA) or potassium t-butoxide (t-BuOK). The lithiated polymers were further reacted to give polymers containing trimethylsilyl-, or diphenylphosphino-groups. The extent of lithiation was found to be critically dependent on the metallating agent, the solvent, and the particular polymer used. Using butyllithium alone, no metallation occurred. Using butyllithium with either TMEDA or t-BuOK lilthiation occurred in cyclohexane, but not when benzene or THF were used as solvents. Preliminary studies indicate that for polystyrene, butyllithium/t-BuOK is significantly more reactive than butyllithium/TMEDA, but the reverse is true for polyacenaphthylene.