Synthesis, chemically and electrochemically polymerization of N-substituted pyrrole containing azo chromophore and its copolymerization with pyrrole

This article describes the synthesis of a novel N-substituted pyrrole monomer containing an azobenzene group. The 2-[N-ethyl-N-[4-[(4-nitrophenyl) azo]-phenyl] amino] ethyl-3-chloropropionate (RedII) compound was synthesized via reaction of 4-nitro-4'-[N-ethyl-N-(2-hydroxyethyl)-amino] azobenzene (RedI) and 3-chloropropionic acid. RedII was reacted with the potassium salt of pyrrole then 2-[N-ethyl-N-[4-[(nitro phenyl) azo] phenyl] amino] ethyl-N-pyrrolyl propionate (Py-RedII) was prepared. Chemical polymerization of Py-RedII and copolymerization of Py-RedII with pyrrole carried out using $FeCl_3$. Poly (2-[N-ethyl-N-[4-[(nitro phenyl) azo] phenyl] amino] ethyl-N-pyrrolyl propionate) (PPy-RedII) was characterized by UV, IR, $^1HNMR$, $^{13}CNMR$ spectroscopies. Electropolymerization of Py-RedII and electroco-polymerization of Py-RedII and pyrrole were studied using conventional three electrodes system, Ag/AgCl reference electrode, platinum counter electrode and GC disk working electrode. Scanning electron microscopy (SEM), thermogravimetry analysis (TGA) and differential scanning calorimetry (DSC) were used for thermal and rheological studies. The TGA curve of PPy-RedII demonstrated a high thermal stability up to 200°C and its DSC thermogram showed two endothermic peaks at 88 and $122^{\circ}C$. The glass transition temperature of the polymer was found to be above the room temperature. Electrical conductivities of PPy-RedII and it's copolymer with pyrrole (PPy-RedII-co-Py) were studied by the four-probe method and produced conductivities of $7.5{\times}10^{-4}$ and $6.5{\times}10^{-3}Scm^{-1}$, respectively.