Highly Stable Anodic Electrochromic Aromatic Polyamides Containing N,N,N‘,N‘-Tetraphenyl-p-Phenylenediamine Moieties: Synthesis, Electrochemical, and Electrochromic Properties

A new triphenylamine-containing aromatic diamine, N,N-bis(4-aminophenyl)-N‘,N‘-di(4-methoxylphenyl)-1,4-phenylenediamine (4), was successfully synthesized by the cesium fluoride-mediated condensation of 4-amino-4‘,4‘ ‘-dimethoxytriphenylamine with 4-fluoronitrobenzene, followed by palladium-catalyzed hydrazine reduction of the dinitro intermediate. A series of novel polyamides with pendent 4,4‘-dimethoxy-substituted triphenylamine (TPA) units having inherent viscosities of 0.28−0.80 dL/g were prepared via the direct phosphorylation polycondensation from the diamine (4) and various dicarboxylic acids. All the polymers were amorphous with good solubility in many organic solvents, such as N-methyl-2-pyrrolidinone (NMP) and N,N-dimethylacetamide (DMAc), and could be solution-cast into tough and flexible polymer films. These aromatic polyamides had useful levels of thermal stability associated with their relatively high softening temperature (242−282 °C), 10% weight-loss temperatures in excess of 510 °C, and c...