The effect of alkyl groups on the polycondensation of aromatic diamines and quinones to form poly(quinone imine)s was investigated. Models were synthesized under standard conditions: I equiv of quinone was reacted with 2 equiv of aniline in the presence of titanium tetrachloride and 1,4-diazabicyclo[2.2.2] octane. Only modest yields of diimines were obtained when alkyl substituents were introduced. Likewise, alkyl substituents were harmful in the polycondensation of both anthraquinones and benzoquinones with aromatic diamines. As for fluorine substituents, model reactions with either 1,5-difluoroanthraquinone or 1,4-difluoroanthraquinone with aniline proceeded in high yields. These model compounds for aromatic poly(quinone imine)s were characterized with H-1 NMR spectroscopy, F-19 NMR spectroscopy, variable-temperature H-1 NMR spectroscopy, and X-ray crystal structure determination. Polymers of the difluoroanthraquinones with aromatic diamines were obtained in high yields, although not in high molecular weights, and no stereocontrol was found. Both p-benzoquinones and anthraquinones were used as monomers in these polymerizations, and a fundamental difference in reactivity was observed. With the former, the polymerization behaved as a classical polycondensation and demanded exact reagent equivalence. With the anthraquinones, however, the polymerization proceeded by a condensation chain polymerization and was much more forgiving.