Archive / Volume LXXVIII 2025

Оlena АKSIMENTYEVA, Nataliia ZHURINA, Yuliia MARKIV, Yaroslav KOVALSKYI

Ivan Franko National University of Lviv, Kyryla i Mefodiya Str., 6, 79005 Lviv, Ukraine
е-mail: nataliia.zhurina@lnu.edu.ua

DOI:

PARTICULARITY OF FORMATION AND SENSORY PROPERTIES OF COPOLIMERS OF ANILINE AND ANISIDINE ON OPTICALLY TRANSPARENT SURFACES

The development of modern industry and the strengthening of requirements for environmental monitoring cause an urgent need for the creation of new generations of highly sensitive, selective, and stable chemical sensors. The detection of various gaseous environments is an important task for the safety and survival of living organisms, especially in conditions of military operations and in contaminated areas. In this regard, optical gas sensors based on conjugated polymer systems are quite effective, as they can promptly signal the presence of toxic substances in "field conditions" and do not require complex equipment or high-energy consumption. Thin films of polyaniline, poly(o-anisidine), and their copolymers were formed by the in situ oxidative polymerization method on the surface of tin (IV) oxide at various monomer ratios in the reaction mixture. Quantum-chemical calculations for o-anisidine and its oligomers (up to the tetramer inclusive) were performed using the semi-empirical PM7 method in the MOPAC2016 program. The initial geometry of the molecules was set using ChemSketch, and the Winmostar V11 graphical interface was used to control the calculations and for visualization. It was established that during the polymerization of o-anisidine, with an increase in the length of the oligomer chain, there is a regular decrease in the ionization potential and a narrowing of the energy gap (the difference in energies of the highest occupied and lowest unoccupied molecular orbitals), which causes the process to auto-accelerate. The kinetic curves of the polymerization of aniline, o-anisidine, and their copolymers (at aniline to anisidine ratios of 1:1 and 3:1 in the reaction mixture) were obtained by monitoring the change in the optical density of the reaction mixture over time at λ = 750 nm. In the study of the kinetics of (co)polymerization, significant differences in the reactivity of the monomers were revealed, as well as an increase in the induction period and a slowdown in the process rate with an increase in the o-anisidine content in the monomer mixture. The gas-sensitive properties of the obtained films were tested with respect to the action of ammonia. It was shown that the sensory response of the materials to the action of ammonia is caused by the reversible deprotonation of the polymer chain, which is accompanied by significant changes in the optical absorption spectra. It was found that the copolymer film with an aniline to o-anisidine ratio of 3:1 demonstrates the highest sensitivity (261%).

Keywords: poly(o-anisidine), polyaniline, copolymers, ammonia, optical spectra.

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