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Kinetic and thermochemical study of the oxidative polymerization of α-substituted styrenes

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Abstract

This article reports a systematic kinetic study on the oxidative polymerization of α-substituted styrene monomers such as styrene (St), α-methylstyrene (AMS), 4-chloro α-methylstyrene (CAMS), and α-phenylstyrene (APS) in the presence of 2,2′-azobisisobutyronitrile as a free radical initiator at 100 psi oxygen pressure and 40-50 °C in toluene. The rate of oxidative polymerization follows the order: APS > CAMS > AMS > St. Theoretical calculations have been performed using density functional theory to support the order of oxidative polymerization rates. In addition, the synthesis and characterization of poly(4-chloro α-methylstyrene peroxide) (PCAMSP) is reported here for the first time. Elemental analysis and nuclear magnetic resonance spectroscopy confirm the alternating copolymer structure of PCAMSP with –O–O– bonds in the main chain. Thermal degradation studies using differential scanning calorimeter and thermogravimetric analysis reveal that PCAMSP degrades highly exothermically and the average enthalpy of degradation at various heating rates is found to be 48.7 ± 0.6 kcal/mol, which is of the same order reported for other vinyl polyperoxides.

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Acknowledgment

The authors gratefully acknowledge the partial financial support from Indian Institute of Science Education and Research-Kolkata and Council of Scientific and Industrial Research (CSIR), New Delhi [01(2474)/11/EMR-II]. Sunirmal Pal acknowledges CSIR, Government of India for his fellowship. PKG would like to thank Department of Science and Technology, India (Project No. SR/FT/CS86/2009) for financial support.

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  1. Department of Chemical Sciences, Indian Institute of Science Education and Research-Kolkata, Nadia, Mohanpur, 741252, West Bengal, India

    Sunirmal Pal, Pradip Kr. Ghorai & Priyadarsi De

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  1. Sunirmal Pal
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  2. Pradip Kr. Ghorai
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  3. Priyadarsi De
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Correspondence to Priyadarsi De.

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Pal, S., Ghorai, P.K. & De, P. Kinetic and thermochemical study of the oxidative polymerization of α-substituted styrenes. Polym. Bull. 69, 149–161 (2012). https://doi.org/10.1007/s00289-011-0697-3

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  • DOI: https://doi.org/10.1007/s00289-011-0697-3

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