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Quantum-Chemical Study of Stressed Polyethylene and Butadiene Rubber Chain Scission

  • Chemical Physics of Polymer Materials
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Abstract

The thermal decomposition of polyethylene and butadiene rubber chains in the presence of a tensile force acting along the axis of the molecule was simulated. The reaction of an isolated chain was considered. The chain models were the octane and 2,6-octadiene molecules. A deformation was introduced in the problem by fixing nonequilibrium distances between the terminal carbon atoms. The reaction coordinate (the middle C–C bond length R) was scanned at a fixed length of the molecule (L). That is, the potential energy surface section of the reaction was constructed at L = const. The reaction sensitivity to deformation was evaluated by B3LYP, LC-ωPBE, CCSD(T), CASSCF, and MP2 quantum-chemical calculations. All these calculations showed that the molecule elongated by ~1 Å for polyethylene, but shortened by 0.3–0.5 Å for 2,6-octadiene during chain scission. This means that the tensile deformation accelerates the decomposition of polyethylene, but decelerates the decomposition of butadiene rubber.

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Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432, Russia

    B. E. Krisyuk

  2. Plekhanov Russian University of Economics, Moscow, 117997, Russia

    E. A. Mamin & A. A. Popov

  3. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Moscow, 119334, Russia

    E. A. Mamin & A. A. Popov

Authors
  1. B. E. Krisyuk
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  2. E. A. Mamin
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  3. A. A. Popov
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Correspondence to B. E. Krisyuk.

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Original Russian Text © B.E. Krisyuk, E.A. Mamin, A.A. Popov, 2018, published in Khimicheskaya Fizika, 2018, Vol. 37, No. 4, pp. 82–90.

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Krisyuk, B.E., Mamin, E.A. & Popov, A.A. Quantum-Chemical Study of Stressed Polyethylene and Butadiene Rubber Chain Scission. Russ. J. Phys. Chem. B 12, 300–307 (2018). https://doi.org/10.1134/S1990793118020185

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  • DOI: https://doi.org/10.1134/S1990793118020185

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