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Radical polymerization of butadiene mediated by molecular iodine: a kinetic study of solution homopolymerization

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Abstract

Homopolymerization of butadiene (Bu) in 1,4-dioxane (Dox) was performed at 70 °C using molecular iodine (I2) in the presence of 4,4’-azobis(4-cyanovaleric acid) (ACVA), resulting in α-carboxyl ω-iodine heterotelechelic polybutadiene. Effect of Dox concentration, molar ratio of ACVA to I2 and initiator type on the Bu conversion was studied. Inhibition of the reaction by molecular I2 was observed until complete consumption of the I2 (induction period). Then, polymerization initiated by carboxyl- functionalized alkyl iodides in situ generated during induction period. ACVA decomposition rate constant (kd), induction time \(\left({t}_{ind}\right)\) and \({k}_{p}^{2}/{k}_{t}\) ratio were calculated using Bu conversion as a function of time data. A good agreement between the theoretical and experimental changes in the conversion versus time was observed, indicating accuracy of the kinetic parameters estimated in this work. Experimental \({t}_{ind}\) was always less that theoretical one. It was attributed to reaction between Bu and I2, resulting in butadiene diiodide (I-Bu-I) compound. Formation of I-Bu-I species was further confirmed by 1H-NMR analysis of end functional groups (i.e. alkyl iodide and allyl iodide) of polybutadiene chains. Based on the 1H-NMR analysis, [I-Bu-I]/[I2]0 ratio was obtained for reaction B4 to be 0.235. It was found that among 1,2 and 1,4 additions, 1,2 addition of I2 to Bu is the dominant reaction. Exchange constant between the growing and dormant species (Cex) was estimated using GPC and conversion data to be in the range of 3.20–3.94. Then, \({M}_{n}\) and \(D\) evolution with conversion was investigated theoretically. Fraction of \(\alpha -\) carboxyl, \(\omega-\) iodide heterotelechelic PBu chains \(\left({f}_{HOOC-PBu-I}\right)\) relative to all chains was estimated from 1H-NMR data to be 87% for reaction B4.

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Acknowledgements

The author, M. Abdollahi, would like to acknowledge the Iran National Science Foundation (INSF) (grant number # 96010037) and Tarbiat Modares University, Tehran, Iran, for the financial support.

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  1. Polymer Reaction Engineering Department, Faculty of Chemical Engineering, Tarbiat Modares University, P.O. Box, 14115-114, Tehran, Islamic Republic of Iran

    Mahdi Abdollahi & Masoud Akbari Hajiataloo

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Abdollahi, M., Akbari Hajiataloo, M. Radical polymerization of butadiene mediated by molecular iodine: a kinetic study of solution homopolymerization. J Polym Res 28, 311 (2021). https://doi.org/10.1007/s10965-021-02617-8

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