Aniline Black is perhaps the oldest known synthetic polymer. It has been studied since the mid 19ᵗʰ century, and is still a matter of interest. These interests arise from the fact that Aniline Black is inexpensive, yet has some very unusual and potentially useful electrical properties. The present approach has been a systematic study of Aniline Black related compounds. The model compounds were synthesized in a controlled fashion to dictate exact structure and purity. It is expected that the better the process of formation, the more uniform the structure, and hence a more usable material as an organic semiconductor. In the course of this investigation conclusions were drawn as to the structure/function aspects of the derived compounds. Attempts to alter the structure of model compounds deviated from the hypothesized behavior. Starburst model compounds displayed properties unexpected to the investigators. Available information about starburst polymers is very scarce. This work complements previous work on Aniline Black and related compounds, and adds a new source of knowledge in starburst chemistry. The properties of starburst compounds can be predicted only in part from the chemical makeup of the materials; this study gives some of the predictions based on the morphology. Several new approaches to the synthesis of useful Aniline Black model compounds grew from the knowledge obtained during this research. These will be presented with the body of the work and discussed at the conclusion as to the significance of such an investigation.

Aniline Black, a polymer containing p-benzoquinodiimine groups, was synthesized chemically or electrochemically by the oxidation of aniline. The polymer salts showed the conductivity of 10⁻¹-10⁻³ ohm⁻¹cm⁻¹. Polymers containing anthroquinodiimine units were also prepared by polycondensations. The syntheses of model compounds containing p-benzoquinodiimine were attempted. Multiazobisphenol monomers were synthesized. 4,4'-(3,3'-Dimethyl-4,4'-biphenylenebisazo) bisphenol 7, 4,4'-[azobis(p-phenyleneazo)] bisphenol 8, and 4,4'-(2-methoxy-1,4-phenylenebisazo) bisphenol 10 displayed liquid crystal (l.c.) properties, while model derivatives of 7, 8, and 4,4'-(4,4'-stilbenebisazo) bisphenol 9 did likewise. Monomers and derivatives of 4-[(4-hydroxyphenyl)azo]-1-naphthol 5, and 4,4'- [oxybis(p-phenyleneazo)] bisphenol 6 showed no l.c. behavior. New thermotropic polyesters based on these multiazobisphenols were synthesized. Sebacates of 5, 6, 7, 8, and 10 showed l.c. behavior, while polymers based on isophthalic or 5-t-butylisophthalic acid did not do so. Polyformals were also synthesized from these momoners, only that of 4 showed weak l.c. behavior. The correlation between the structure of these polymers and their tractabilities, electrical properties, liquid crystal behaviors was studied. Polymers and copolymers containing p-azoarylene and p-azoxyarylene groups were synthesized by oxidative coupling of various aromatic diamines. Films were cast directly from the reaction mixtures or from the polymer solution. The films were n-doped by sodium naphthalide or p-doped by iodine. They showed electrical conductivities of 10⁻⁴ to 10⁻⁵ ohm⁻¹cm⁻¹. AB monomers containing dipolar p-phenyleneazo groups were synthesized: 4-(4-hydroxy-2-methoxyphenylazo) benzoic acid 21, 4-[4-(4-hydroxy-2-methoxyphenylazo)-2-methoxyphenylazo] benzoic acid 22, and 4-(4-hydroxy-2-methoxyphenylazo)-3-nitrobenzoic acid 23. The monomers were polymerized by direct polycondensations. The polyester synthesized from 21 formed a red, transparent film. A polymethacrylate containing dipolar p-phenyleneazo groups in the side chains was also prepared by the free radical polymerization of 1- [3-methoxy-4-(p-nitrophenylazo)-phenoxy] hexyl methacrylate 28.