NOVEL POLYAROMATIC QUINONE IMINES

A novel synthetic route to poly(quinone imines) has been developed. Reaction of anthraquinone (AQ) with aromatic diamines in the presence of titanium tetrachloride and 1,4-diazabicyclo-[2.2.2]octane (Dabco) as base in refluxing chloro- or o-dichlorobenzene led to high molecular weight polymers with the poly(quinone diimine) structure. Polymerization of AQ with methylene-4,4'-dianiline resulted in a mixture of high molecular weight polymer (M(w), 15 000) and oligomeric macrocycles. The polymerization of AQ was also accomplished with 4,4'-oxy- and 4,4'-thiodianiline, as well as with p-phenylenediamine. The latter polymer is the dibenzo analog of the pernigraniline base form of polyaniline. tert-Butylanthraquinone was also successfully used as a comonomer with the various aromatic diamines. All these polymers are red in color, soluble in organic solvents, and film-forming. Polymerizations of the aromatic diamines with heterocyclic-substituted benzoquinones, such has benzo[1,2-b:4,5-b']dithiophene-4,8-dione, 2,2'-dialkylbenzo[1,2-d:5,4-d']dioxazole-4,8-dione, and N,N',2,2'-tetraalkylbenzo-[1,2-d:5,4-d']imidazole-4,8-dione, were also investigated.