Polímeros: Ciência e Tecnologia
Polímeros: Ciência e Tecnologia
Original Article

PVC plasticizer from trimethylolpropane trioleate: synthesis, properties, and application

Laura de Andrade Souza; Edson Luiz Francisquetti; Rafael Domingos Dalagnol; Celso Roman Junior; Maria Telma Gomes Schanz; Martin Edmund Maier; Cesar Liberato Petzhold

Downloads: 0
Views: 87


A new oleic acid derivative plasticizer, epoxidized trimethylolpropane trioleate (EPO), has been synthesized and its application in PVC formulations compared with di(2-ethylhexyl) 1,2-cyclohexanoate (DOCH/DEHCH), a commercial phthalate-free plasticizer of petrochemical origin. EPO and their blends with DOCH were added to PVC resin (50 PHR) and the plasticized PVC has been characterized by thermal and mechanical measurements. EPO demonstrated good compatibility with the PVC resin improving the thermal stability and elongation at break. Due to EPO high molar mass, a slight increase in the glass transition temperature and hardness was observed as the content of EPO in the plasticizer blend increased. The results indicate that EPO is a potential plasticizer for PVC when pure and, by replacing 50% of DOCH, the PVC compound shows similar properties to pure DOCH, but better elongation at break and thermal stability.


plasticizers, PVC, renewable sources, epoxidized trimethylpropane trioleate, dioctyl cyclohexanoate


1 Hosney, H., Nadiem, B., Ashour, I., Mustafa, I., & El‐Shibiny, A. (2018). Epoxidized vegetable oil and bio‐based materials as PVC plasticizer. Journal of Applied Polymer Science, 135(20), 46270. http://dx.doi.org/10.1002/app.46270.

2 Shah, B. L., & Shertukde, V. V. (2003). Effect of plasticizers on mechanical, electrical, permanence, and thermal properties of poly (vinyl chloride). Journal of Applied Polymer Science, 90(12), 3278-3284. http://dx.doi.org/10.1002/app.13049.

3 Unar, I. N., Soomro, S. A., & Aziz, S. (2010). Effect of various additives on the physical properties of polyvinylchloride resin. Pakistan Journal of Analytical & Environmental Chemistry, 11(2), 44-50. Retrieved in 2020, December 17, from http://pjaec.pk/index.php/pjaec/article/view/107/117

4 Daniels, P. H. (2009). A brief overview of theories of pvc plasticization and methods used to evaluate pvc‐plasticizer interaction. Journal of Vinyl & Additive Technology, 15(4), 219-223. http://dx.doi.org/10.1002/vnl.20211.

5 Latini, G., De Felice, C., & Verrotti, A. (2004). Plasticizers, infant nutrition and reproductive health. Reproductive Toxicology (Elmsford, N.Y.), 19(1), 27-33. http://dx.doi.org/10.1016/j.reprotox.2004.05.011. PMid:15336709.

6 Tan, J., Zhang, S., Lu, T., Li, R., Zhong, T., & Zhu, X. (2019). Design and synthesis of ethoxylated esters derived from waste frying oil as anti-ultraviolet and efficient primary plasticizers for poly (vinyl chloride). Journal of Cleaner Production, 229, 1274-1282. http://dx.doi.org/10.1016/j.jclepro.2019.04.395.

7 Radke, E. G., Galizia, A., Thayer, K. A., & Cooper, G. S. (2019). Phthalate exposure and metabolic effects: a systematic review of the human epidemiological evidence. Environment International, 132, 104768. http://dx.doi.org/10.1016/j.envint.2019.04.040. PMid:31196577.

8 Tickner, J. A., Schettler, T., Guidotti, T., McCally, M., & Rossi, M. (2001). Health risks posed by use of Di‐2‐ethylhexyl phthalate (DEHP) in PVC medical devices: a critical review. American Journal of Industrial Medicine, 39(1), 100-111. http://dx.doi.org/10.1002/1097-0274(200101)39:1<100::AID-AJIM10>3.0.CO;2-Q. PMid:11148020.

9 Bui, T. T., Giovanoulis, G., Cousins, A. P., Magnér, J., Cousins, I. T., & de Wit, C. A. (2016). Human exposure, hazard and risk of alternative plasticizers to phthalate esters. The Science of the Total Environment, 541, 451-467. http://dx.doi.org/10.1016/j.scitotenv.2015.09.036. PMid:26410720.

10 Colle, K. S., Stanat, J. E. R., Reinoso, J. J., & Godwin, S. (2010). US Patent No. 20100305250A1. USA: USPTO. Retrieved in 2020, December 17, from https://patents.google.com/patent/US20100305250A1/en

11 Ou, Y., Ding, X., & Zhang, L. (2014). Synthesis and application of an alternative plasticizer Di (2‐Ethylhexyl)‐1, 2‐cyclohexane dicarboxylate. Journal of Applied Polymer Science, 131(2), n/a. http://dx.doi.org/10.1002/app.39763.

12 Hou, L., Fan, C., Liu, C., Qu, Q., Wang, C., & Shi, Y. (2018). Evaluation of repeated exposure systemic toxicity test of PVC with new plasticizer on rats via dual parenteral routes. Regenerative Biomaterials, 5(1), 9-14. http://dx.doi.org/10.1093/rb/rbx020. PMid:29423263.

13 Hab, S. A., Talpur, F. N., Baig, J. A., Afridi, H. I., Surhio, M. A., & Talpur, M. K. (2018). Leaching and exposure of phthalates from medical devices; health impacts and regulations. Environmental Contaminants Reviews, 1(2), 13-21. http://dx.doi.org/10.26480/ecr.02.2018.13.21.

14 Schilling, C. L. 3rd, & Kelly, K. K. (2018). U.S. Patent US:.2018/0105673 A1. Kingsport: U.S. Patent and Trademark Office.

15 Mizik, T., & Gyarmati, G. (2021). Economic and sustainability of biodiesel production: a systematic literature review. Cleanroom Technology, 3(1), 19-36. http://dx.doi.org/10.3390/cleantechnol3010002.

16 Jamarani, R., Erythropel, H. C., Nicell, J. A., Leask, R. L., & Marić, M. (2018). How green is your plasticizer? Polymers, 10(8), 834. http://dx.doi.org/10.3390/polym10080834. PMid:30960759.

17 Karmalm, P., Hjertberg, T., Jansson, A., Dahl, R., & Ankner, K. (2009). Network formation by epoxidised soybean oil in plastisol poly (vinyl chloride). Polymer Degradation & Stability, 94(11), 1986-1990. http://dx.doi.org/10.1016/j.polymdegradstab.2009.07.029.

18 Mao, D., Chaudhary, B. I., Sun, B., Shen, C.-Y., Yuan, D., Dai, G.-C., Li, B., & Cogen, J. M. (2015). Absorption and migration of bio‐based epoxidized soybean oil and its mixtures with tri (2‐ethylhexyl) trimellitate in poly (vinylchloride). Journal of Applied Polymer Science, 132(19), n/a. http://dx.doi.org/10.1002/app.41966.

19 Chaudhary, B. I., Nguyen, B. D., Smith, P., Sunday, N., Luong, M., & Zamanskiy, A. (2015). Bis (2‐ethylhexyl) succinate in mixtures with epoxidized soybean oil as bio‐based plasticizers for poly (vinylchloride). Polymer Engineering and Science, 55(3), 634-640. http://dx.doi.org/10.1002/pen.23934.

20 Coltro, L., Pitta, J. B., da Costa, P. A., Fávaro Perez, M. Â., de Araújo, V. A., & Rodrigues, R. (2014). Migration of conventional and new plasticizers from PVC films into food simulants: a comparative study. Food Control, 44, 118-129. http://dx.doi.org/10.1016/j.foodcont.2014.03.058.

21 Choi, M. S., Rehman, S. U., Kim, H., Han, S. B., Lee, J., Hong, J., & Yoo, H. H. (2018). Migration of epoxidized soybean oil from polyvinyl chloride/polyvinylidene chloride food packaging wraps into food simulants. Environmental Science and Pollution Research International, 25(5), 5033-5039. http://dx.doi.org/10.1007/s11356-017-0951-9. PMid:29273993.

22 Jia, P., Xia, H., Tang, K., & Zhou, Y. (2018). Plasticizers derived from biomass resources: a short review. Polymers, 10(12), 1303. http://dx.doi.org/10.3390/polym10121303. PMid:30961228.

23 Jia, P., Zhang, M., Hu, L., & Zhou, Y. (2016). Green plasticizers derived from soybean oil for poly (vinyl chloride) as a renewable resource material. Korean Journal of Chemical Engineering, 33(3), 1080-1087. http://dx.doi.org/10.1007/s11814-015-0213-9.

24 Zheng, T., Wu, Z., Xie, Q., Fang, J., Hu, Y., Lu, M., Xia, F., Nie, Y., & Ji, J. (2018). Structural modification of waste cooking oil methyl esters as cleaner plasticizer to substitute toxic dioctyl phthalate. Journal of Cleaner Production, 186, 1021-1030. http://dx.doi.org/10.1016/j.jclepro.2018.03.175.

25 Kandula, S., Stolp, L., Grass, M., Woldt, B., & Kodali, D. (2017). Functionalization of soy fatty acid alkyl esters as bio plasticizers. Journal of Vinyl & Additive Technology, 23(2), 93-105. http://dx.doi.org/10.1002/vnl.21486.

26 Moreira, D. R., Chaves, P. O. B., Ferreira, E. N., Arruda, T. B. M. G., Rodrigues, F. E. A., Câmara, J. F. No., Petzhold, C. L., Maier, M. E., & Ricardo, N. M. P. S. (2020). Moringa polyesters as eco-friendly lubricants and its blends with naphthalenic lubricant. Industrial Crops and Products, 158, 112937. http://dx.doi.org/10.1016/j.indcrop.2020.112937.

27 American Society for Testing and Materials – ASTM. (2014). ASTM D1239–14: Standard Test Method for Resistance of Plastic Films to Extraction by Chemicals. West Conshohocken: ASTM.

28 Brasil. Ministério da Saúde. Agência Nacional de Vigilância Sanitária – ANVISA. Resolução nº 105, de 19 de maio de 1999 (1999, 20 maio). Aprova os Regulamentos Técnicos: Disposições Gerais para Embalagens e Equipamentos Plásticos em contato com Alimentos. Diário Oficial da República Federativa do Brasil, Brasília.

29 Danov, S. M., Kazantsev, O. A., Esipovich, A. L., Belousov, A. S., Rogozhin, A. E., & Kanakov, E. A. (2017). Recent advances in the field of selective epoxidation of vegetable oils and their derivatives: a review and perspective. Catalysis Science & Technology, 7(17), 3659-3675. http://dx.doi.org/10.1039/C7CY00988G.

30 Köckritz, A., & Martin, A. (2008). Oxidation of unsaturated fatty acid derivatives and vegetable oils. European Journal of Lipid Science and Technology, 110(9), 812-824. http://dx.doi.org/10.1002/ejlt.200800042.

31 Noor Armylisas, A. H., Siti Hazirah, M. F., Yeong, S. K., & Hazimah, A. H. (2017). Modification of olefinic double bonds of unsaturated fatty acids and other vegetable oil derivatives via epoxidation: a review. Grasas y Aceites, 68(1), 174. http://dx.doi.org/10.3989/gya.0684161.

32 Cheong, M., Hasan, Z. A. A., & Idris, Z. (2019). Characterisation of epoxidised trimethylolpropane trioleate: NMR and thermogravimetric analysis. Journal of Oil Palm Research, 31(1), 146-158. http://dx.doi.org/10.21894/jopr.2018.0066.

33 Monteavaro, L. L., da Silva, E. O., Costa, A. P. O., Samios, D., Gerbase, A. E., & Petzhold, C. L. (2005). Polyurethane networks from formiated soy polyols: synthesis and mechanical characterization. Journal of the American Oil Chemists’ Society, 82(5), 365-371. http://dx.doi.org/10.1007/s11746-005-1079-0.

34 Suzuki, A. H., Botelho, B. G., Oliveira, L. S., & Franca, A. S. (2018). Sustainable synthesis of epoxidized waste cooking oil and its application as a plasticizer for polyvinyl chloride films. European Polymer Journal, 99, 142-149. http://dx.doi.org/10.1016/j.eurpolymj.2017.12.014.

35 Kim, J. R., & Sharma, S. (2012). The development and comparison of bio-thermoset plastics from epoxidized plant oils. Industrial Crops and Products, 36(1), 485-499. http://dx.doi.org/10.1016/j.indcrop.2011.10.036.

36 Borugadda, V. B., & Goud, V. V. (2016). Physicochemical and rheological characterization of waste cooking oil epoxide and their blends. Waste and Biomass Valorization, 7(1), 23-30. http://dx.doi.org/10.1007/s12649-015-9434-8.

37 Chen, J., Liu, Z., Nie, X., & Jiang, J. (2018). Synthesis and application of a novel environmental C26 diglycidyl ester plasticizer based on castor oil for poly (vinyl chloride). Journal of Materials Science, 53(12), 8909-8920. http://dx.doi.org/10.1007/s10853-018-2206-7.

38 Tong, H., & Hai, J. (2019). Sustainable synthesis of bio‐based hyperbranched ester and its application for preparing soft polyvinyl chloride materials. Polymer International, 68(3), 456-463. http://dx.doi.org/10.1002/pi.5730.

39 Bocqué, M., Voirin, C., Lapinte, V., Caillol, S., & Robin, J. J. (2016). Petro‐based and bio‐based plasticizers: chemical structures to plasticizing properties. Journal of Polymer Science, Part A: Polymer Science, 54(1), 11-33. http://dx.doi.org/10.1002/pola.27917.

40 Ang, D. T. C., Khong, Y. K., & Gan, S. N. (2016). Palm oil‐based compound as environmentally friendly plasticizer for poly (vinyl chloride). Journal of Vinyl & Additive Technology, 22(1), 80-87. http://dx.doi.org/10.1002/vnl.21434.

41 Tan, J., Liu, B., Fu, Q., Wang, L., Xin, J., & Zhu, X. (2019). Role of the oxethyl unit in the structure of vegetable oil-based plasticizer for PVC: an efficient strategy to enhance compatibility and plasticization. Polymers, 11(5), 779. http://dx.doi.org/10.3390/polym11050779. PMid:31052451.

42 Jia, P., Zhang, M., Hu, L., Feng, G., Bo, C., & Zhou, Y. (2015). Synthesis and application of environmental castor oil based polyol ester plasticizers for poly (vinyl chloride). ACS Sustainable Chemistry & Engineering, 3(9), 2187-2193. http://dx.doi.org/10.1021/acssuschemeng.5b00449.

43 Omrani, I., Ahmadi, A., Farhadian, A., Shendi, H. K., Babanejad, N., & Nabid, M. R. (2016). Synthesis of a bio-based plasticizer from oleic acid and its evaluation in PVC formulations. Polymer Testing, 56, 237-244. http://dx.doi.org/10.1016/j.polymertesting.2016.10.027.

44 Ma, Y., Song, F., Hu, Y., Kong, Q., Liu, C., Rahman, M. A., Zhou, Y., & Jia, P. (2020). Highly branched and nontoxic plasticizers based on natural cashew shell oil by a facile and sustainable way. Journal of Cleaner Production, 252, 119597. http://dx.doi.org/10.1016/j.jclepro.2019.119597.

45 Feng, G., Ma, Y., Zhang, M., Jia, P., Liu, C., & Zhou, Y. (2019). Synthesis of bio-base plasticizer using waste cooking oil and its performance testing in soft poly (vinyl chloride) films. Journal of Bioresources and Bioprodcts, 4(2), 99-110. http://dx.doi.org/10.21967/jbb.v4i2.214.

46 Schiller, M. (2015). PVC additives: performance, chemistry, developments, and sustainability. Munich: Carl Hanser Verlag. http://dx.doi.org/10.3139/9781569905449.

47 Mehta, B., Kathalewar, M., & Sabnis, A. (2014). Diester based on castor oil fatty acid as plasticizer for poly (vinyl chloride). Journal of Applied Polymer Science, 131(11), 40354. http://dx.doi.org/10.1002/app.40354.

48 Feng, G., Hu, L., Ma, Y., Jia, P., Hu, Y., Zhang, M., Liu, C., & Zhou, Y. (2018). An efficient bio-based plasticizer for poly (vinyl chloride) from waste cooking oil and citric acid: synthesis and evaluation in PVC films. Journal of Cleaner Production, 189, 334-343. http://dx.doi.org/10.1016/j.jclepro.2018.04.085.

49 Yu, J., Sun, L., Ma, C., Qiao, Y., & Yao, H. (2016). Thermal degradation of PVC: a review. Waste Management (New York, N.Y.), 48, 300-314. http://dx.doi.org/10.1016/j.wasman.2015.11.041. PMid:26687228.

50 Marongiu, A., Faravelli, T., Bozzano, G., Dente, M., & Ranzi, E. (2003). Thermal degradation of poly (vinyl chloride). Journal of Analytical and Applied Pyrolysis, 70(2), 519-553. http://dx.doi.org/10.1016/S0165-2370(03)00024-X.

51 Wang, Y., Nie, X., & Li, X. (2016). Synthesis and characterization of novel pentaerythritol ester as PVC plasticizer. Journal of Applied Polymer Science, 133(47), 44227. http://dx.doi.org/10.1002/app.44227.

61a6210ea953950b4d5d3fd4 polimeros Articles
Links & Downloads

Polímeros: Ciência e Tecnologia

Share this page
Page Sections