Effect of organic solvents on the functionalization of liquid natural rubber by iron salt-mediated chloro-nitro reaction
85 viewsDOI:
https://doi.org/10.54939/1859-1043.j.mst.IPE.2024.40-49Keywords:
Functionalization; Chloro-nitro; Cl-N-LNR.Abstract
This study presents the functionalization process and the effect of organic solvents on the iron salt-mediated chloro-nitro reaction. The product obtained from the reaction is the chloro-nitro compound of liquid natural rubber (Cl-N-LNR). LNR functionalization was achieved by NO2Cl radical formed from iron(III) nitrate nonahydrate and iron(III) chloride in various organic solvents including ethyl acetate (EtOAc), tetrahydrofuran (THF), and dioxane (DOX). Fourier-transform infrared spectroscopy (FT-IR) was used to evaluate the structure of the resulting Cl-N-LNR. The degree of functionalization with the nitro group is 13÷15% mol units of Cl-N-LNR and the efficiency of the chlorine-nitration reaction is 80÷90%. Depending on the type of solvent used for the reaction, the structures of the functionalized chains received are disparate. Notably, the Cl-N-LNR is made in a THF/DOX solvent mixture that exhibited superior properties compared to the other solvents.
References
[1]. Khai D. M., & Nhan, P. D., "Effect of some experimental factors on preparation of liquid natural rubber", Vietnam Journal of Science and Technology, 54, 563-569, (2016).
[2]. Nor H. M. a. J. R. E., "Pergamon LIQUID NATURAL RUBBER", Progress in Polymer Science, 23, 143-177, (1998)`.
[3]. Saetung A., "Preparation of polyurethane foams from Hydroxytelechelic oligoisoprenes obtained by controlled degradation of natural rubber: study of their physico-mechanical, thermal, and acoustic properties", Université du Maine, (2009),
[4]. Baharulrazi N., Hussin Mohd Nor, and Wan Khairuddin Wan Ali., "Hydroxyl terminated natural rubber (HTNR) as a binder in solid rocket propellant", Applied Mechanics and Materials, 695, 174-178, (2015).
[5]. Onn M., Nor, H., & Wan Ali, W., "Development of solid rocket propellant based on isophorone diisocyanate–hydroxyl terminated natural rubber binder", Jurnal Teknologi (Sciences and Engineering), 69, 53-58, (2014).
[6]. Doan K. M., Tuan, N. M., Anh, N. T., & Nhan, P. D., "Evaluation of the characteristics of plastic explosive adhered by liquid natural rubber", Vietnam Journal of Science and Technology, 58, 557-564, (2020).
[7]. Cheng T., "Review of novel energetic polymers and binders–high energy propellant ingredients for the new space race", Designed Monomers and Polymers, (2019),
[8]. Abdullah M., Gholamian, F., & Zarei, A. R., "Investigation of composite solid propellants based on nitrated hydroxyl-terminated polybutadiene binder", Journal of Propulsion and Power, 30, 862-864, (2014).
[9]. Colclough M. E., Desai, H., Millar, R. W., Paul, N. C., Stewart, M. J., & Golding, P., "Energetic polymers as binders in composite propellants and explosives", Polymers for Advanced Technologies, 5, 554-560, (1994).
[10]. Sudarma I. M., Wazni, N., Wildawaty, N., Yuanita, E., & Suana, I. W., "An efficient method on nitration of eugenol using NH4NO3 and KHSO4", Asian Journal of Chemistry, 26, 173, (2014).
[11]. Zelenov V. P., & Lobanova, A. A., "Nitration of primary aminofurazans with aqueous nitric acid", Russian Chemical Bulletin, 60, 334-338, (2011).
[12]. Olah G. A., Malhotra, R., & Narang, S. C., "Nitration: methods and mechanisms", Across Conventional Lines: Selected Papers of George A Olah, 2, 975-979, (2003).
[13]. Su B. H. D., "Nitration of Diene Polymers", University of Massachusetts Amherst, (1983),
[14]. Taniguchi T., Fujii, T., & Ishibashi, H., "Iron-mediated radical halo-nitration of alkenes", The Journal of Organic Chemistry, 75, 8126-8132, (2010).
[15]. Costa S. A., "Nitration of Alkenes and Conjugated Dienes Using Lithium Nitrate/Trifluoroacetic Anhydride", Doctoral dissertation, Drexel University, (2016),
[16]. Doan K. M., Tran, T. B., Kim, H. D., Dam, H. Q., Nguyen, T. D., & Ly, V. Q., "Functionalization of a liquid natural rubber by iron‐mediated radical chloro‐nitration and its thermal decomposition", Vietnam Journal of Chemistry, 62, 61-67, (2024).
[17]. Wieczorek-Ciurowa K., & Kozak, A., "The thermal decomposition of Fe (NO 3) 3· 9H 2 O", Journal of Thermal Analysis and Calorimetry, 58, 647-651, (1999).
[18]. Chen D., Shao, H., Yao, W., & Huang, B., "Fourier transform infrared spectral analysis of polyisoprene of a different microstructure", International Journal of Polymer Science, 937284, (2013).
[19]. Müller M., Villalba, J. C., & Anaissi, F. J., "Decomposição térmica (TG-DTA) de sais de ferro [FeCl3.6H2O] e [Fe (NO3)3.9H2O] com análise morfológica e química do produto final", Semina: Ciências Exatas e Tecnológicas, 35, 9-14, (2014).
[20]. Smallwood I., "Handbook of organic solvent properties", Butterworth-Heinemann, (2012),
[21]. Kowalska T., Kaczmarski, K., & Prus, W., "Theory and mechanism of thin-layer chromatography", Handbook of Thin-Layer Chromatography, 86-129, (2003).
[22]. Jiang X., Zhai, Y., Chen, J., Han, Y., Yang, Z., & Ma, S., "Iron‐Catalyzed Aerobic Oxidation of Aldehydes: Single Component Catalyst and Mechanistic Studies", Chinese Journal of Chemistry, 36, 15-19, (2018).
[23]. Beckett M. A., & Hua, I., "Elucidation of the 1, 4-dioxane decomposition pathway at discrete ultrasonic frequencies", Environmental science & technology, 34, 3944-3953, (2000).
[24]. Colclough M. E., & Paul, N. C., "Nitrated hydroxy-terminated polybutadiene: synthesis and properties", 97-103, (1996).
