Thermodynamics of phase transitions of esters as an indicator of migration stability of plasticizers in PVC
Keywords:
adipate, hysteresis, migration, model, Einstein paradigm, plasticizer, polyvinyl chloride, phase transition, enthalpyAbstract
The paper presents a thermodynamic approach to the design of new unsymmetric adipate plasticizers for PVC. The phase transitions of synthesized esters containing phenoxy and butoxy substituents were studied using differential scanning calorimetry. It was found that the aromatic fragment causes high melting points and significant transition enthalpies, while the aliphatic analogs are liquids. A quantitative assessment of the hysteresis of phase transitions has been carried out, which reaches 76 °C for phenoxy-substituted esters, which directly indicates the kinetic barriers during crystallization associated with a complex molecular structure. It has been shown that this parameter is a critical indi-cator that allows for the prediction of the tendency of the plasticizer to migrate and sweat out of the PVC matrix during operation. Based on the obtained data, criteria have been formulated for selecting compounds that ensure the long-term stability of polymer compositions. The research results provide a scientific basis for developing effective and stable alternatives to traditional phthalate plasticizers. A mathematical model of plasticizer migration based on the generalized Einstein paradigm is pro-posed, which describes the transfer of matter in the PVC-plasticizer systemReferences
1. Гроссман Ф. Руководство по разработке композиций на основе ПВХ. М.: Научные основы и технологии, 2009. 550 с.
2. Барштейн Р.С., Кириллович В.И., Носовский Ю.Е. Пластификаторы для полимеров. М.: Химия, 1982. 196 с.
3. Daniels P.H. // J. Vinyl. Addit. Technol. 2009. V. 15, № 4. P. 219. DOI: 10.1002/vnl.20211
4. Кербер М.Л., Виноградов В.Л., Головкин Г.С, Горбаткина О.А., Крыжановский В.К., Ку-перман А.М, Симонов-Емельянов И.Д., Xaлиулин В.И., Бунаков В.А. Полимерные композиционные материалы: структура, свойства, технология. СПб.: Профессия, 2008. 506 с.
5. Matthews G. PVC: production, properties and uses, volume 587. Institute of Materials London, 1996. 379 р.
6. Козлов Н.А., Митрофанов А.Д. Физика полимеров. Владимир: Владим. гос. ун-т, 2001. 345 с.
7. Schiller M. PVC additives: performance, chemistry, developments, and sustainability. Munich: Carl Hanser Verlag GmbH Co KG, 2022. 503 р.
8. Власов С.В., Кандырин Л.Б., Кулезнев В.Н. Основы технологии переработки пластмасс: учебник. М.: Химия, 2004. 600 с.
9. Osswald T.A., Hernandes-Ortiz J.P. Polymer processing: Modelling and simulation. Munich: Hanser Publ., 2006. 606 p.
10. Швецов Г.А., Алимова Д.У., Барышникова М.Д. Технология переработки пластических масс: учебник для техникумов. М.: Химия, 1988. 512 с.
11. Vikhareva I.N., Manojlović D. // Applied Sciences. 2024. V. 14(23). Р. 10953. DOI: 10.3390/app142310953
12. Vikhareva I.N., Kruchinina P.A., Manojlović D. // Polymers. 2024. V. 16(23). P. 3372. DOI: 10.3390/polym16233372
13. Vikhareva I.N., Abramian A., Manojlović D., Bol'shakov O. // Polymers. 2025. V. 17(15). Р. 2140. DOI: 10.3390/polym17152140
14. Krock R.P., Schiller M., Frenkel P., Summers J.W., Daniels C.A. PVC. Encyclopedia of Poly-mer Science and Technology. 4th ed. Hoboken: John Wiley & Sons, 2011. 255 p.
15. Minale Y.F., Getnet T., Negawo T.A., Bitew M.A. // Polymers. 2025. V. 17, No. 9. P. 1149. DOI: 10.3390/polym17091149
16. Han Y., Weng Y., Zhang C. // Journal of Vinyl and Additive Technology. 2024. V. 30, No. 1. P. 26. DOI: https://doi.org/10.1002/vnl.22048
17. Lei Q., Zhang Y., Gao Y., Zhou B., Wu G., Hao X., Chen L., Wang R. // Polymers. 2025. V. 17, No. 12. P. 1655. DOI: 10.3390/polym17121655
18. Czogała J., Pankalla E., Turczyn R. // Materials. 2021. V. 14, No. 4. P. 844. DOI: 10.3390/ma14040844
19. Теплофизические и реологические характеристики полимеров: справ. / под ред. Ю.С. Ли-патова. Киев: Наукова думка, 1977. 244 с.
20. Крыжановский В.К., Бурлов В.В., Паниматченко А.Д., Крыжановская Ю.В. Технические свойства полимерных материалов: уч.-справ. пос. СПб.: Профессия, 2003. 240 с.
21. Вихарева И.Н., Кручинина П.А., Еникеева Д.В., Шарапова И.Т., Николаев Д.В. // Вестник ЮУрГУ. Серия «Химия». 2024. Т. 16, № 4. С. 144. DOI: 10.14529/chem240414
22. Mazitova A.K., Aminova G.K., Vikhareva I.N. // Polymers. 2021. V. 13. 1761. DOI: 10.3390/polym13111761.
23. Gao Y., Yu L., Yeo J.C., Lim C.T. // Advanced Materials. 2020. V. 32, No. 15. P. 1902133. DOI: 10.1002/adma.202070117
24. Czogała J., Pankalla E., Turczyn R. // Materials. 2021. V. 14, No. 4. P. 844. DOI: 10.3390/ma14040844
25. Titow W.V. PVC plastics: properties, processing, and applications. London: Springer Science & Business Media, 2012. 902 p.
26. Liu C. et al. // Progress in Polymer Science. 2024. V. 152. P. 101815. DOI: 10.1016/j.progpolymsci.2024.101815
27. Schurr J.M., Fujimoto B.S., Huynh L., Chiu D.T. // J. Phys. Chem. B. 2013. Vol. 117. P. 7626–7652.
28. Einstein A. // Ann. Phys. Leipzig. 1905. Bd. 322. S. 549–560.
29. Skorokhod A.V. Basic principles and applications of probability theory. Berlin, Heidelberg: Springer, 2005. 282 p.
30. Landau L.D., Lifshitz E.M. Fluid Mechanics. Vol. 6. Oxford: Pergamon Press, 1987. 537 p.
31. Rubin Y. // Water Resources Research. 1991. Vol. 27, No. 7. P. 1723.
32. Zimmermann U., Schneider H., Wegner L.H., Haase A. // New Phytologist. 2004. V. 162, No. 3. P. 575.
33. Hoang L., Ibragimov A. // Journal of Mathematical Analysis and Applications. 2026. V. 560, Iss. 2. DOI: 10.1016/j.jmaa.2026.130489
34. Hida T. Brownian Motion. New York: Springer-Verlag, 1980. 325 p
