Design and preparation of novel fluorescent polyimides containing ortho-linked units and pyridine moieties

A novel pyridine-containing aromatic diamine monomer, 4-[4-hydroxyphenyl]-2,6-bis[4-(2-aminophenoxy)phenyl]pyridine (p,o-HAPP), was synthesized by a modified Chichibabin reaction of p-Hydroxybenzaldehyde and a substituted acetophenone, 4-(2-nitrophenoxy)acetophenone (p,o-NPAP), followed by a reduction of the resulting dinitro compound 4-[4-hydroxyphenyl]-2,6-bis[4-(2-nitrophenoxy)phenyl]pyridine with Pd/C and hydrazine monohydrate. The aromatic diamine was employed to prepare a series of pyridine-containing polyimides (PIs) by polycondensation with various aromatic dianhydrides in N,N-dimethylformamide (DMF) via the conventional two-step method. The inherent viscosities of the resulting poly(amic acids) and PIs were in range of 0.62–0.76 and 0.52–0.64 dL/g, respectively. The obtained novel PIs exhibited high solubility in common organic solvents, such as m-Cresol, DMF, N,N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone (NMP), tetrahydrofuran, and chloroform. Meanwhile, flexible PI films were obtained, which had excellent thermal stability, with the glass transition temperature (T g) of 259.8–323.4 °C and the temperature at 10% weight loss of 485.5–576.4 °C in nitrogen atmosphere. The protonated polymer showed UV–vis absorption in the region 200–400 nm and displayed strong fluorescence intensity (470 nm) in NMP solution.