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

Quantum-Chemical Study of Stressed Polyethylene and Butadiene Rubber Chain Scission 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. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Russian Journal of Physical Chemistry B Springer Journals

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

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Publisher
Springer Journals
Copyright
Copyright © 2018 by Pleiades Publishing, Ltd.
Subject
Chemistry; Physical Chemistry
ISSN
1990-7931
eISSN
1990-7923
DOI
10.1134/S1990793118020185
Publisher site
See Article on Publisher Site

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.

Journal

Russian Journal of Physical Chemistry B – Springer Journals

Published: May 29, 2018

References

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