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

Your Location：

Home >

Browse articles >

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

RESEARCH ARTICLE | Updated：2026-07-25

- Molecular Dynamics Investigation of the Mechanism of Poly(vinyl chloride) Plasticization by Dicarboxylic Acid Esters
- Chinese Journal of Polymer Science Vol. 44, Pages: 1-13(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：2026-06
- Accepted：
Scan QR Code
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. https://doi.org/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/OL]. Chinese Journal of Polymer Science, 2026, 441-13.
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. https://doi.org/10.1007/s10118-026-3736-0 DOI：

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/OL]. Chinese Journal of Polymer Science, 2026, 441-13. DOI： 10.1007/s10118-026-3736-0.

摘要

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.

关键词

Keywords

references

Rahman, M., Brazel, C. The plasticizer market: an assessment of traditional plasticizers and research trends to meet new challenges. Prog. Polym. Sci. 2004 , 29 , 1223−1248..

Ali, M., Ueki, T., Hirai, T., Sato, T., Sato, T. Dielectric and electromechanical studies of plasticized poly(vinyl chloride) fabricated from plastisol. Polym. Int. 2013 , 62 , 501−506..

[Titow, W.V. in PVC Technology , Springer, Dordrecht, 1984 , p. 59..

[Wypych, G. in PVC Formulary , 3rd ed., ChemTec Publishing, Toronto, 2020 , p. 47..

Wang, M.Y., Zhou, N.Q., Hu, J. Effect of plasticizer (DOP) on cell structure and mechanical properties of extrusion-foamed PVC sheet. Mater. Sci. Forum 2015 , 815 , 601−606..

Tickner, J.A., Schettler, T., Guidotti, T., McCally, M., Rossi, M. Health risks posed by use of di-2-ethylhexyl phthalate (DEHP) in pvc medical devices: a critical review. Am. J. Ind. Med. 2001 , 39 , 100−111..

Gartili, A., Lapinte, V., Caillol, S., Briou, B., Jego, L. CNSL-based plasticizers, a promising and sustainable alternative to phthalates, a review. RSC Sustain. 2025 , 3 , 81−111..

Bocqúe, M., Voirin, C., Lapinte, V., Caillol, S., Robin, J. Petro-based and bio-based plasticizers: Chemical structures to plasticizing properties. J. Polym. Sci. A Polym. Chem. 2015 , 54 , 11−33..

Perito, E.D., Guerra, N.B., Giovanela, M., Machado, G., Silva Crespo, J. Chemical, thermal and mechanical evaluation of poly(vinyl chloride) plastisol with different plasticizers. J. Elastomers Plast. 2022 , 54 , 1277−1294..

Chen, Y., Zhou, S., Pan, S., Zhao, D., Wei, J., Zhao, M., Fan, H. Methods for determination of plasticizer migration from poly(vinyl chloride) synthetic materials: a mini review. J. Leather Sci. Eng. 2022 , 4 , 8..

Daniels, P.H. A brief overview of theories of PVC plasticization and methods used to evaluate PVC-plasticizer interaction. J. Vinyl Addit. Technol. 2009 , 15 , 219−223..

Misra, M., Mannodi-Kanakkithodi, A., Chung, T.C., Ramprasad, R., Kumar, S.K. Critical role of morphology on the dielectric constant of semicrystalline polyolefins. J. Chem. Phys. 2016 , 144 , 234905..

Ramos, J., Vega, J.F., Martínez-Salazar, J. A new insight into the conformation and melt dynamics of hydrogenated polybutadiene as revealed by computer simulations. Soft Matter 2016 , 12 , 3929−3936..

[Mao, Y. F., Long, S. N., Li, Z., Tao, W. Q. Diffusion behavior of VOC molecules in poly(vinyl chloride) investigated by molecular dynamics simulation. Int. J. Environ. Res. Public Health 2023 , 20 , 3235..

Li, J., Jin, S. H., Lan, G. C., Xu, Z. S., Wang, L. T., Wang, N., Li, L. J. Research on the glass transition temperature and mechanical properties of poly(vinyl chloride)/dioctyl phthalate (PVC/DOP) blends by molecular dynamics simulations. Chinese J. Polym. Sci. 2019 , 37 , 834−840..

Lei, Q., Yi, X., Yu, W., Cheng, J., Ou, S., Xue, Q., Jiang, H. Molecular dynamics simulation of plasticizing effect of mixed dioctyl phthalate and isosorbide diheptanoate on poly(vinyl chloride) material. Polymers 2025 , 17 , 1655..

Dongyang Li, D., Panchal, K., Mafi, R. Xi, L. An atomistic evaluation of the compatibility and plasticization efficacy of phthalates in poly(vinyl chloride). Macromolecules 2018 , 51 , 6997−7012..

Li, D., Panchal, K., Vasudevan, N.K., Mafi, R. Xi, L. Effects of molecular design parameters on plasticizer performance in poly(vinyl chloride): a comprehensive molecular simulation study. Chem. Eng. Sci. 2022 , 249 , 117334..

Zhou, Y., Milner, S.T. Average and Local Tg Shifts of Plasticized PVC from Simulations. Macromolecules 2018 , 51 , 3865−3873..

Wang, J., Wolf, R. M., Caldwell, J. W., Kollman, P. A., Case, D. A. Development and testing of a general amber force field. J. Comput. Chem. 2004 , 25 , 1157−1174..

Bayly, C.I., Cieplak, P., Cornell, W., Kollman, P.A. A well-behaved electrostatic potential based method using charge restraints for deriving atomic charges: the RESP model. J. Phys. Chem. 1993 , 97 , 10269−10280..

Neese, F. The ORCA program system. Wiley Interdiscip. Rev. Comput. Mol. Sci. 2012 , 2 , 73−78..

Neese, F. Software update: the ORCA program system, version 4.0. Wiley Interdiscip. Rev. Comput. Mol. Sci. 2018 , 8 , e1327..

[Abraham, M.J., Murtola, T., Schulz, R., Pall, S., Smith, J.C., Hess, B., Lindahl, E. GROMACS: High performance molecular simulations through multi-level parallelism from laptops to supercomputers. SoftwareX 2015 , 1-2 , 19–25..

Bussi, G., Donadio, D., Parrinello, M. Canonical sampling through velocity rescaling. J. Chem. Phys. 2007 , 126 , 014107−014106..

Berendsen, H.J.C., Postma, J.P.M., Gunsteren, W.F., DiNola, A., Haak, J.R. Molecular dynamics with coupling to an external bath. J. Chem. Phys. 1984 , 81 , 3684−3690..

Hess, B., Bekker, H., Berendsen, H.J.C., Fraaije, J.G.E.M. LINCS: A linear constraint solver for molecular simulations. J. Comput. Chem. 1997 , 18 , 1463−1472..

Darden, T., York, D., Pedersen, L. Particle mesh Ewald: An Nlog(N) method for Ewald sums in large systems. J. Chem. Phys. 1993 , 98 , 10089−10092..

Wennberg, C.L., Murtola, T., Hess, B., Lindahl, E. Lennard–Jones lattice summation in bilayer simulations has critical effects on surface tension and lipid properties. J. Chem. Theory Comput. 2013 , 9 , 3527−3537..

Vikhareva, I.N., Manojlovíc, D. The effect of the structure of the alcohol component on the plasticizing ability of the ester of aliphatic dicarboxylic acid. Appl. Sci. 2024 , 14 , 10953..

Vikhareva, I.N., Kruchinina, P., Manojlovíc, D. The effect of dicarboxylic acid structure on the plasticizing ability of its ester. Polymers 2024 , 16 , 3372..

Makarov, G., Borodina, O., Makarova, T., Ignatova, A., Olivenko, N., Bartashevich, E., Sapozhnikov, S. Molecular dynamics study of cured ED-20 epoxy resin for predicting the glass transition temperature and relationship with structure features. J. Phys. Chem. A 2023 , 127 , 3894−3905..

Makarov, G. I., Deriabin, K. V., Islamova, R. M., Bartashevich, E. V. Structural organization of the self-healing copolymers of polydimethylsiloxane and Ni(II)pyridinedicarboxamide by the molecular dynamics and fragment condensation approach. J. Inorg. Organomet. Polym. Mater. 2025 , 35 , 5133−5143..

Notay, Y. Flexible conjugate gradients. SIAM J. Sci. Comput. 2001 , 22 , 1444−1460..

Liu, D.C., Nocedal, J. On the limited memory BFGS method for large scale optimization. Math. Program. 1989 , 45 , 503−528..

Daura, X., Gademann, K., Jaun, B., Seebach, D., Gunsteren, W.F., Mark, A.E. Peptid e folding: when simulation meets experiment. Angew. Chem. Int. Ed. 1999 , 38 , 236−240..

Desiraju, G.R., Shing Ho, P., Kloo, L., Legon, A.C., Marquardt, R., Metrangolo, P., Politzer, P., Resnati, G., Rissanen, K. Definition of the halogen bond (IUPAC recommendations 2013). Pure Appl. Chem. 2013 , 85 , 1711−1713..

Bondi, A. Van der Waals volumes and radii. J. Phys. Chem. 1964 , 68 , 441−451..

Lourenço, T.C., Coelho M.F.C., Ramalho, T.C., van der Spoel, D., Costa, L.T. Insights on the solubility of CO 2 in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide from the microscopic point of view. Environ. Sci. Technol. 2013 , 47 , 7421−7429..

Makarov, G.I. Molecular dynamics simulation of the electrical conductivity of α,ω-bis(3-aminopropyl) polydimethylsiloxane. Mendeleev Commun. 2025 , 35 , 1−4..

Parrinello, M., Rahman, A. Polymorphic transitions in single crystals: a new molecular dynamics method. J. Appl. Phys. 1981 , 52 , 7182−7190..

Vikhareva, I.N., Aminova, G.K., Mazitova, A.K. Ecotoxicity of the adipate plasticizers: influence of the structure of the alcohol substituent. Molecules 2021 , 26 , 4833..

Vikhareva, I. N.; Aminova, G. K.; Mazitova, A. K. Development of a highly efficient environmentally friendly plasticizer. Polymers 2022 , 14 , 1888..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Plasticizing and Strengthening Poly(vinyl chloride) with Structurally Different Ionic Liquids

The Effect of Polymerization of Ionic Liquid [C4Vim]Br on Phase Behavior and Partitioning of L-tryptophan: Experimental and Molecular Dynamics Study

Plasticizer Enhanced Chain Orientation and Dynamics for Printed Stretchable Conjugated Polymer Films

Dynamic Supramolecular Polymer Networks Constructed by Synergistic Dual Host-Guest Interactions

Hypercrosslinked Porous Organic Polymers from Tetraaniline and Anthraquinone for High-capacitance, Long-life Supercapacitors

Related Author

Xiang Gao

Ji-Shuo Ye

Zhi-Ji Liu

Jian Wu

Ning-Zhong Bao

Petr A. Korchak

Evgenia A. Safonova

Igor Yu. Gotlib

Related Institution

School of Engineering, Hangzhou City University

State Key Laboratory of Silicon Materials, School of Materials Science and Engineering, Zhejiang University

State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University

Institute of Chemistry, Saint Petersburg State University, Saint Petersburg

State Key Laboratory of Polymer Science and Technology, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences

⁰