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Molecular dynamics simulation of polystyrene copolymer with octyl short-chain branches in toluene

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Abstract

In this study, dimensional, conformational and dynamic behaviors of a short-chain branched styrene/1-octene copolymer chain with different 1-octene percentages, i.e., 0, 2, 4 and 6%, in toluene are investigated at the temperature of 298.15 K via molecular dynamics simulation. The chain dimensions and flexibility in the solvent are evaluated by calculating the radius of gyration (Rg), end-to-end distance (<r0>), surface area (Ach), and volume (Vch) of the copolymer chain. The mean square displacement (MSD) and diffusivity coefficient for each copolymer chain are measured to determine its dynamic behavior and mobility in aromatic media. To consider the effect of increasing the 1-octene co-monomer percentage on the copolymer chain affinity to the solvent molecules, the interaction energy (Eint) and Flory-Huggins (FH) interaction parameter are calculated for each equilibrated solution model. The simulation results indicate that the co-monomer level increment in the copolymer structure reduces the chain Rg amount and its interaction with the solvent. The <r0> of the chain increases up to 4% co-monomer content, while further co-monomer content decreases the <r0> value. Additionally, the viscosity of the equilibrated dilute solutions is calculated via non-equilibrium molecular dynamics simulation (NEMD). Moreover, the steric hindrance of the copolymers and the solvent molecules capturing in the dilute solution is determined via radial distribution function (RDF) analysis. Helmholtz free energy and the system entropy changes are calculated to evaluate the tendency of the copolymer to the solvent molecules and its dilute solution irregularity, respectively.

The figure shows the variations trend of the poly(styrene-co-1-octene) chain dimensions in toluene aromatic solvent by increasing the 1-octene content (x), after the equilibration state. Red and blue colors represent the carbon atoms of the copolymer chain backbone and 1-octene side chains, respectively. The styrene rings and the hydrogen atoms of the chains were removed for better view.

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Authors and Affiliations

  1. Smart Polymers and Nanocomposites Research Group, School of Chemical Engineering, Iran University of Science and Technology, Tehran, 16846–13114, Iran

    Sajad Rasouli, Mohammad Reza Moghbeli & Sousa Javan Nikkhah

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  1. Sajad Rasouli
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  3. Sousa Javan Nikkhah
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Correspondence to Mohammad Reza Moghbeli.

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Rasouli, S., Moghbeli, M.R. & Nikkhah, S.J. Molecular dynamics simulation of polystyrene copolymer with octyl short-chain branches in toluene. J Mol Model 26, 80 (2020). https://doi.org/10.1007/s00894-020-4339-2

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