Abstract
A new soluble polymer on 2-[(2E)-1-methyl-2-buten-1-yl]aniline and its copolymers with aniline basis have been synthesized in various molar ratios. For all samples, the electrical conductivity, morphology, solubility, electrochemical properties, as well as spectral and molecular mass characteristics have been studied, and a comparative analysis with polyaniline has been carried out. The substituent introduced into the aniline aromatic ring significantly improves the solubility in typical organic solvents of a high molecular weight product. The morphology of the test compounds depends on the co-monomer ratio. As the content of the substituted aniline in the initial mixture increases, the morphology of the polymer changes from the inherent polyaniline fibrous microstructure to the globular one with irregular substituted polyaniline shapes and sizes. Electrochemical study of the samples revealed that the higher the oxidation potential, the wider the band gap (ranging from 2.00 to 2.15). The electrical conductivity decreases in proportion to the increase in the substituted aniline concentration of the initial co-monomer mixture and amounts to 12.5–35.7 × 106 nSm.
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Jarjes, Z.; Samian, M.; AbGhani, S. Conductive polymers: Their preparations and catalyses on NADH oxidation at carbon cloth electrodes. Arab. J. Chem. 2015, 5, 726–731.
Long, Y.; Li, M.; Gu, C.; Wan, M.; Duvail, J.; Liu, Z.; Fan, Z. Recent advances in synthesis, physical properties and applications of conducting polymer nanotubes and nanofibers. Prog. Polym. Sci. 2011, 36, 1415–1442.
Salikhov, R.; Biglova, Y.; Mustafin, A. New organic polymers for solar cells. In Emerging solar energy materials. ed. by Sadia Ameen. IntechOpen 2018, 83–104.
Nicolas-Debarnot, D.; Poncin-Epaillard, F. Polyaniline as a new sensitive layer for gas sensors. Anal. Chim. Acta 2003, 475, 1–15.
Stejskal, J.; Sapurina, I.; Trchova, M. Polyaniline nanostructures and the role of aniline oligomers in their formation. Prog. Polym. Sci. 2010, 35, 1420–1481.
Bhadra, S.; Khastgir, D.; Singha, N. K., Lee, J. H. Progress in preparation, processing and applications of polyaniline. Prog. Polym. Sci. 2009, 34, 783–810.
Ćirić-MarjanoviĆ, G. Recent advances in polyaniline research: Polymerization mechanisms, structural aspects, properties and applications. Synth. Met. 2013, 177, 1–47.
Vivekanandan, J.; Ponnusamy, V.; Mahudeswaran, A.; Vijayanand, P. Synthesis and characterization and conductivity study of polyaniline by chemical oxidative and electrochemical methods. Arch. Appl. Sci. Res 2011, 3, 147–153.
Verma, D. Role of novel microstructure of polyaniline-CSA thin film in ammonia sensing at room temperature. Sens. Actuat. B: Chem. 2008, 134, 373–376.
Shakoor, A.; Rizvi, T.; Sulaiman, M.; Nasir, M.; Ishtiaq, M. Electronic properties of aniline doped with dodecylbenzenesulphonic acid (PANI-DBSA) and poly(methyl methacrylate) (PMMA) blends in the presence of hydroquinone. J. Mater. Sci.: Mater. Electron. 2010, 21, 603–607.
Im, S.; Han, M.; Cho, S.; Oh, S. Preparation and characterization of polyaniline nanoparticles synthesized from DBSA micellar solution. Synth. Met. 2002, 126, 53–60.
Liu, J.; Hu, X.; Wang, X.; Yao, J.; Sun, D.; Fan, Z.; Guo, M. Facile synthesis of hollow microspheres of polyaniline using poly(sodium 4-styrenesulfonic acid) as dopant. Polym. Int. 2014, 63, 722–726.
Summers, G. Conducting polyaniline nanorods doped with aromatic carboxyl chain end functionalized polymers. Synth. Met. 2015, 209, 251–261.
Kabomo, T.; Scurrell, M. The effects of ring substituents in aniline on the reactivity of PANI with hydrogen tetrachloroaurate and the dispersion of gold nanoparticles. Polym. Adv. Technol. 2016, 27, 759–764.
Khamngoen, K.; Paradee, N.; Sirivat, A. Chemical oxidation polymerization and characterization of poly ortho-anisidine nanoparticles. J. Polym. Res. 2016, 23, 172.
Liu, Y.; Li, S.; Yao, P.; Zhang, Q. Synthesis of organic soluble poly(substituted-aniline) from 2-methyl-6-ethylaniline tar. Int. J. Mod. Phys. B 2017, 31, 1744091.
Barbero, C.; Salavagione, H.; Acevedo, D.; Grumelli, D.; Garay, F.; Planes, G.; Miras, M. Novel synthetic methods to produce functionalized conducting polymers I. Polyanilines. Electrochim. Acta 2004, 49, 3671–3686.
Waware, U. The spectral and morphological studies of the conductive polyaniline thin film derivatives by the in situ copolymerization. J. Mater. Sci-Mater. El. 2017, 28, 15178–15183.
Thota, A.; Arukula, R.; Narayan, R.; Rao, C.; Raju, K. V. S. N. Energy storage and surface protection properties of dianiline co-polymers. RSC Adv. 2015, 5, 106523–106535.
Tran, H.; D’Arcy, J.; Wang, Y.; Beltramo, P.; Strong, V.; Kaner, R. The oxidation of aniline to produce “polyaniline”: A process yielding many different nanoscale structures. J. Mater. Chem. 2011, 21, 3534–3550.
Waware, U.; Summers, G.; Hamouda, A. M. S.; Rashid, M. Synthesis and characterization of polyaniline, poly(3-fluoroaniline), and poly(aniline-co-3-fluoroaniline) derivatives obtained by chemical oxidative polymerization methods. Polym. Plast. Technol. Eng. 2017, 57, 1–11.
Movahedifar, F.; Modarresi-Alam, A. The effect of initiators and oxidants on the morphology of poly[(±)-2-(sec-butyl) aniline] a chiral bulky substituted polyaniline derivative. Polym. Adv. Technol. 2016, 27, 131–139.
Teasdale, P.; Spinks, G.; Kane-Maguire, L.; Wallace, G. Conductive electroactive polymers: Intelligent polymer systems. in Conductive electroactive polymers: Intelligent polymer systems, CRC, New York, 2008.
Ortega, E.; Armijo, F.; Jessop, I.; Del Valle, M. A.; Díaz, F. R. Chemical synthesis and characterization of polyaniline derivatives: Substituent effect on solubility and conductivity. J. Chil. Chem. Soc. 2013, 58, 1959–1962.
Biglova, Yu.; Salikhov, R.; Abdrakhmanov, I.; Salikhov, T.; Safargalin, I.; Mustafin, A. Preparation and investigation of soluble functionalized polyanilines. Phys. Solid State 2017, 59, 1228–1233.
Salavagione, H. Preparation and characterization of “clickable” polyaniline derivatives on graphene modified electrodes. J. Electroanal. Chem. 2016, 765, 118–125.
Abdrakhmanov, I.; Mustafin, A.; Sharafutdinov, V. Claisen rearrangement in the series of aromatic amines, Gilem, Ufa, 2014.
Cope, A.; Hardy, E. The introduction of substituted vinyl groups. V. A rearrangement involving the migration of an allyl group in a three-carbon system. J. Am. Chem. Soc. 1940, 62, 441–444.
Abdrakhmanov, I.; Sharafutdinov, V. M.; Tolstikov, G. A. Amino-Kleisen rearrangement as a method for the synthesis of C-cycloalkanilanilines. Bull. Russ. Acad. Sci.: Chem. 1982, 9, 2160.
Gvozdenović, M.; Jugović, B.; Stevanović, J.; Grgur, B. Electrochemical synthesis of electroconducting polymers. Hem. Ind. 2014, 68, 673–684.
Aprano, G.; Leclerc, M.; Zotti, G. Steric and electronic effects in methyl and methoxy substituted polyanilines. J. Electroanal. Chem. 1993, 351, 145–158.
Aprano, G.; Leclerc, M.; Zotti, G.; Schiavon, G. Synthesis and characterization of polyaniline derivatives: Poly(2-alkoxyanilines) and poly(2,5-dialkoxyanilines). Chem. Mater. 1995, 7, 33–42.
Wei, Y.; Focke, W.; Wnek, G.; Ray, A.; MacDiarmid, A. Synthesis and electrochemistry of alkyl ring-substituted polyanilines. J. Phys. Chem. 1989, 93, 495–499.
Aymen, M. Correlation between Raman spectroscopy and electrical conductivity of graphite/polyaniline composites reacted with hydrogen peroxide. J. Phys. D: Appl. Phys. 2013, 46, 335103.
Barbero, C.; Miras, M.; Haas, O.; Kötz, R. Direct in situ evidence for proton/anion exchange in polyaniline films by means of probe beam deflection. J. Electrochem. Soc. 1991, 138, 669–672.
Lindfors, T.; Ivaska, A. pH sensitivity of polyaniline and its substituted derivatives. J. Electroanal. Chem. 2002, 531, 43–52.
Acknowledgments
This work was carried out within the framework of the state task program (No. AAAA-A19-119020890014-7). Electron microscopic studies were performed on the basis of the Center for Collective Use of Scientific Equipment of the Institute of Metal Superplasticity Problems, RAS “Structural and Physico-Mechanical Material Studies”.
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Andriianova, A., Shigapova, A., Biglova, Y. et al. Synthesis and Physico-chemical Properties of (Co)polymers of 2-[(2E)-1-methyl-2-buten-1-yl]aniline and Aniline. Chin J Polym Sci 37, 774–782 (2019). https://doi.org/10.1007/s10118-019-2261-9
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DOI: https://doi.org/10.1007/s10118-019-2261-9