Soluble High-Temperature Polymers Containing a Tetraphenylthiophene Unit

Soluble high-temperature polymers containing a tetraphenylthiophene unit were successfully prepared. Four types of tetraphenylthiophene monomers—diamine, diisocyanate, dicarboxylic acid chloride, and dibromide—were synthesized starting from tetraphenylthiophene, which was readily obtained by the reaction of benzyl chloride and sulfur. Aromatic polyimides and copolyimides were prepared by the reactions of tetraphenylthiophene diamine with tetracarboxylic dianhydrides, tetraphenylthiophene diisocyanate with tetracarboxylic dianhydrides, and tetraphenylthiophene diamine with tetracarboxylic dithioanhydrides. Aromatic polyamides and copolyamides were obtained from the reaction pairs of tetraphenylthiophene diamine and dicarboxylic acid chlorides, tetraphenylthiophene dicarboxylic acid chloride and diamines, and tetraphenylthiophene dibromide, diamines, and carbon monoxide. Similarly aromatic polyamide-imides were prepared by the reaction of tetraphenylthiophene diamine with 4-chloroformylphthalic anhydride, and tetraphenylthiophene diisocyanate with trimellitic anhydride. The reaction of tetraphenylthiophene dicarboxylic dichloride with bisphenols and aminophenols afforded aromatic polyesters and polyamide-esters, respectively. Aromatic polyazomethines were prepared by the reaction of tetraphenylthiophene diamine and dialdehydes. All the polymers were obtained in high molecular weights, and all were soluble in organic solvents and had high glass transition temperatures around 300°C.