Copolymer Formation Between Two N‐Substituted Anilines—Electrochemical and Spectroelectrochemical Studies

Abstract

Electrochemical polymerization of diphenylamine, DPA with N-methyl aniline, NMA was performed using cyclic voltammetry in a 4 M sulfuric acid medium. The electrochemical parameters representing the polymer deposition showed a strong dependence on the molar concentration ratios of DPA or NMA in the feed. In situ spectroelectrochemical studies were performed during the electropolymerization with different molar concentration feed ratios of DPA. The results reveal the formation of intermediates together with DPA and NMA units. Derivative cyclic voltabsorptograms (DCVAs) were deduced at the wavelength of absorbance corresponding to the intermediates and explained with redox characteristics in cyclic voltammogram. Results from cyclic voltammetry and spectroelectrochemical studies favor copolymer formation between DPA and NMA. Copolymers were prepared for different molar concentrations feed ratios of DPA and the composition of the monomer units in the copolymers were determined. Reactivity ratios of DPA and NMA were deduced using Fineman-Ross and Kelen-Tudos methods and correlated with the results from cyclic voltammetry and spectroelectrochemical studies.

Novel Copolymer-based Electrochemical Sensor for the Facile Determination of Biomarkers of Diabetes and Hepatocellular Carcinoma

“…This shift of redox peaks in the later scan of CVs of pLCys-MES/GCE in comparison with that of individual monomers may be due to the electrooxidation and reduction of more dimers or oligomers than monomers. 50,51 The oxidation peak seen at 1.05 V of MES polymerisation merged with the oxidation peak of L-Cys. This indicated the inclusion of a greater number of monomer, dimer or oligomer units at the later stages of electropolymerisation.…”

“…This indicated the inclusion of a greater number of monomer, dimer or oligomer units at the later stages of electropolymerisation. 51 Thus, thyil free radical and primary amine free radical formed in case of first cyclic scan of LCys and H 2 C-O., -CH 2 -C.H 2 radical in case of MES respectively reacts with themselves or each other in a number of ways. If it combines with themselves resulting to self-polymerisation or they can undergo cross reaction forming new LCys and MES units.…”

“…52 This results in the formation of different dimers or oligomers during the later scans. 50,51 In order to predict the structure of the final copolymer, all these possibilities have to be considered and the final product formed may also depend on the individual monomer concentration in the mixed solution, potential at which each radical is formed 52 etc.…”

Aqueous Electrosyntheses of Homo and Copolymers of Pyrrole and Aniline in a Binary Electrolyte System

“…The latter is assigned to polaronic and bipolaronic transitions of aniline unit in the polymeric chain. [56][57][58] However, these absorption bands ͑i.e., at 450 and 800-1000 nm͒ seem to diminish with decreases in the conductivity. 40 In other medium ͑PAni prepared in PTSA without KCl͒ ͑Fig.…”

Electrochemical synthesis and spectroelectrochemical behavior of poly(diphenylamine-co-4,4′-diaminodiphenyl sulfone)

“…Yang et al [17] performed electrochemical copolymerization of diphenylamine (DPA) with 2,5-dimethoxyaniline (DMA) in 4 M H 2 SO 4 for different feed ratios of DPA using cyclic voltammetry. Gopalan et al [18][19][20][21][22] obtained copolymerization of diphenylamine with differently substituted anilines using cyclic voltammetry and pulse potentiostatic (PSSM) methods and reported the spectroelectrochemical behavior of the copolymers.…”