Molecular Dynamics Investigation of the Mechanism of Poly(vinyl chloride) Plasticization by Dicarboxylic Acid Esters

Gennady I. Makarov; Irina N. Vikhareva; Oleg I. Bol’shakov

doi:10.1007/s10118-026-3736-0

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Molecular Dynamics Investigation of the Mechanism of Poly(vinyl chloride) Plasticization by Dicarboxylic Acid Esters

RESEARCH ARTICLE | Updated：2026-09-23

- Molecular Dynamics Investigation of the Mechanism of Poly(vinyl chloride) Plasticization by Dicarboxylic Acid Esters
- Chinese Journal of Polymer Science Vol. 44, Issue 10, Pages: 3597-3609(2026)
- Affiliations：
  
  a.South Ural State University, 76, Lenin prospekt, Chelyabinsk 454080, Russia
  b.Nanotechnology Education and Research Center, South Ural State University, 76, Lenin prospekt, Chelyabinsk 454080, Russia
  c.Laboratory of Cell Hemostasis, National Medical Research Centre of Cardiology named after Academician E.I. Chazov of the Ministry of Health of the Russian Federation, 15A, Akademika Chazova st., Moscow 121552, Russia
- Author bio：
  
  makarovgi@susu.ru
- Funds：
- DOI：10.1007/s10118-026-3736-0
  CLC：
- Received：17 March 2026，
  
  Accepted：05 May 2026，
  
  Online First：24 July 2026，
  
  Published：05 October 2026
- Accepted：
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Makarov, G. I.; Vikhareva, I. N.; Bol’shakov, O. I. Molecular dynamics investigation of the mechanism of poly(vinyl chloride) plasticization by dicarboxylic acid esters. Chinese J. Polym. Sci. 2026, 44, 3597–3609

Gennady I. Makarov, Irina N. Vikhareva, Oleg I. Bol’shakov. Molecular Dynamics Investigation of the Mechanism of Poly(vinyl chloride) Plasticization by Dicarboxylic Acid Esters[J]. Chinese Journal of Polymer Science, 2026, 44(10): 3597-3609.
Makarov, G. I.; Vikhareva, I. N.; Bol’shakov, O. I. Molecular dynamics investigation of the mechanism of poly(vinyl chloride) plasticization by dicarboxylic acid esters. Chinese J. Polym. Sci. 2026, 44, 3597–3609 DOI： 10.1007/s10118-026-3736-0.

Gennady I. Makarov, Irina N. Vikhareva, Oleg I. Bol’shakov. Molecular Dynamics Investigation of the Mechanism of Poly(vinyl chloride) Plasticization by Dicarboxylic Acid Esters[J]. Chinese Journal of Polymer Science, 2026, 44(10): 3597-3609. DOI： 10.1007/s10118-026-3736-0.

摘要

The structure of poly(vinyl chloride) (PVC) plasticized with dicarboxylic acid diesters (dibutoxyethyl glutarate

dibutoxyethyl adipate

octyl butoxyethyl adipate

dibutoxyethyl azelate

and dibutoxyethyl sebacate) was studied using molecular dynamics simulations. A transition from a plasticization mechanism associated with Cl···O interactions

which is characteristic of short-chain diesters

to a mechanism of volumetric dispersive distribution of PVC chains for long-chain esters was identified.

Abstract

Polymer compositions based on plasticized poly(vinyl chloride) (PVC) are extremely widely used in engineering and everyday life. Diester plasticizers based on aliphatic dicarboxylic acids are currently considered as new

environmentally friendly

and less toxic plasticizers for poly(vinyl chloride). In the present work

the structural organization of polymer compositions based on poly(vinyl chloride) plasticized with dicarboxylic acid diesters—dibutoxyethyl glutarate

dibutoxyethyl adipate

octyl butoxyethyl adipate

dibutoxyethyl azelate

and dibutoxyethyl sebacate—was studied using molecular dynamics modeling methods. The methodology of fragment condensation was used to obtain three-dimensional models of the dense polymer phase. It is shown that the intensity of intermolecular interactions between PVC chains and plasticizer molecules

as well as the degree of uniformity of the plasticizer’s spatial distribution

directly affect the characteristics of the temperature dependence of the mechanical loss tangent. Thereby

the heterogeneity of the plasticizer distribution at the nanoscale level

determined by its tendency to associate

significantly affects the width of the glass transition. The data suggest a possible transition from a plasticization mechanism characteristic of short-chain diesters (associated with a higher number of directional Cl···O contacts) to a mechanism of bulk dispersion spacing of PVC chains for long-chain esters. This interpretation is consistent with the observed differences in thermal stability and low-temperature flexibility. These conclusions are based on a limited set of five plasticizers and a specific MD/fragment-condensation framework; therefore

they should be considered as preliminary and model-dependent.

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