Skip to main content
SpringerLink
Log in

Preparation and evaluation of acetylated mixture of citrate ester plasticizers for poly(vinyl chloride)

  • Original Research
  • Published:
Iranian Polymer Journal Aims and scope Submit manuscript

Abstract

Tributyl citrate (TBC) and acetyl tributyl citrate (ATBC), as phthalate alternative plasticizers, show limited application due to low migration resistance, high volatilization rate and intense respiratory irritation. Meanwhile, the developed pure citrates, such as butyryl trihexyl citrate (BTHC) due to its high cost, and triisooctyl citrate (TOC) and acetyl triisooctyl citrate (ATOC) due to their low absorption property, are not attractive plasticizers to manufacture phthalate-free poly(vinyl chloride)s (PVCs). In this study, we developed an effective method to synthesize acetylated mixture of citrate esters (ATMC) composed of acetyl (dibutyl-monoisooctyl) citrate, acetyl (monobutyl-diisooctyl) citrate, and a small amount of ATBC and ATOC, as an alternative for phthalate plasticizers. ATMC combines the advantages of ATBC in being easily absorbed and ATOC in having good migration resistance. Characterization results showed that the dynamic viscosity, absorption property and plasticizing efficiency of ATMC11 (1:1 molar ratio of n-butyl alcohol to 2-ethylhexanol) were similar to those of di(2-ethylhexyl) phthalate (DEHP). The thermal volatilization and migration of ATMC11 were less than those of ATBC, and were comparable to those of DEHP, which could be attributed to the improved compatibility with PVC. The performance of ATMC11 was improved compared with that of the mixture of ATBC and ATOC. As an environmental bio-based plasticizer, ATMC11 was demonstrated as a biologically safe plasticizer by biological safety evaluation tests. Therefore, ATMC11 with excellent comprehensive performances and low cost can be candidate as an ideal phthalate alternative for soft PVC formulations.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. de Espinosa LM, Gevers A, Woldt B, Grass M, Meier MAR (2014) Sulfur-containing fatty acid-based plasticizers via thiol-ene addition and oxidation: synthesis and evaluation in PVC formulations. Green Chem 16:1883–1896

    Article  Google Scholar 

  2. Bocque M, Voirin C, Lapinte V, Caillol S, Robin J (2016) Petro-based and bio-based plasticizers: chemical structures to plasticizing properties. J Polym Sci Polym Chem 54:11–33

    Article  CAS  Google Scholar 

  3. Net S, Rabodonirina S, Sghaier RB, Dumoulin D, Chbib C, Tlili I, Ouddane B (2015) Distribution of phthalates, pesticides and drug residues in the dissolved, particulate and sedimentary phases from transboundary rivers (France–Belgium). Sci Total Environ 521–522:152–159

    Article  CAS  PubMed  Google Scholar 

  4. Tran BC, Teil MJ, Blanchard M, Alliot F, Chevreuil M (2015) BPA and phthalate fate in a sewage network and an elementary river of France: influence of hydroclimatic conditions. Chemosphere 119:43–51

    Article  CAS  PubMed  Google Scholar 

  5. Souza FL, Sáez C, Cañizares P, Motheo AJ, Rodrigo MA (2013) Sonoelectrolysis of wastewaters polluted with dimethyl phthalate. Ind Eng Chem Res 52:9674–9682

    Article  CAS  Google Scholar 

  6. Wang J, Chen G, Christie P, Zhang M, Luo Y, Teng Y (2015) Occurrence and risk assessment of phthalate esters (PAEs) in vegetables and soils of suburban plastic film greenhouses. Sci Total Environ 523:129–137

    Article  CAS  PubMed  Google Scholar 

  7. Cheng X, Ma L, Xu D, Cheng H, Yang G, Luo MJ (2015) Mapping of phthalate esters in suburban surface and deep soils around a metropolis-Beijing, China. J Geochem Explor 155:56–61

    Article  CAS  Google Scholar 

  8. Di Gennaro P, Collina E, Franzetti A, Lasagni M, Luridiana A, Pitea D, Bestetti G (2005) Bioremediation of diethylhexyl phthalate contaminated soil: a feasibility study in slurry—and solid-phase reactors. Environ Sci Technol 39:325–330

    Article  CAS  PubMed  Google Scholar 

  9. Blanchard O, Glorennec P, Mercier F, Bonvallot N, Chevrier C, Ramalho O, Mandin C, Bot BL (2014) Semivolatile organic compounds in indoor air and settled dust in 30 french dwellings. Environ Sci Technol 48:3959–3969

    Article  CAS  PubMed  Google Scholar 

  10. Kang Y, Man YB, Cheung KC, Wong MH (2012) Risk assessment of human exposure to bio-accessible phthalate esters via indoor dust around the Pearl River Delta. Environ Sci Technol 46:8422–8430

    Article  CAS  PubMed  Google Scholar 

  11. Guo Y, Kannan K (2011) Comparative assessment of human exposure to phthalate esters from house dust in china and the United States. Environ Sci Technol 45:3788–3794

    Article  CAS  PubMed  Google Scholar 

  12. Simoneit BRT, Medeiros PM, Didyk BM (2005) Combustion products of plastics as indicators for refuse burning in the atmosphere. Environ Sci Technol 39:6961–6970

    Article  CAS  PubMed  Google Scholar 

  13. Eckert E, Müller J, Göen TJ (2015) Simultaneous determination of polyvinylchloride plasticizers di(2-ethylhexyl) phthalate and tri(2-ethylhexyl) trimellitate and its degradation products in blood by liquid chromatography-tandem mass spectrometry. Chromatogr A 1410:173–180

    Article  CAS  Google Scholar 

  14. You L, Wang Y, Zeng Q, Huang MY, Hu Y, Cao W, Liu A, Lu W (2015) Semen phthalate metabolites, spermatozoa apoptosis, and DNA damage: a cross-sectional study in china. Environ Sci Technol 49:3805–3812

    Article  CAS  PubMed  Google Scholar 

  15. Ishii S, Katagiri R, Minobe Y, Kuribara I, Wada T, Wada M, Imai S (2015) Investigation of the amount of transdermal exposure of newborn babies to phthalates in paper diapers and certification of the safety of paper diapers. Regul Toxicol Pharm 73:85–92

    Article  CAS  Google Scholar 

  16. Ni X, Xing X, Cao Y, Cao G (2016) Determination of phthalates in food packing materials by electrokinetic chromatography with polymeric pseudostationary phase. Food Chem1 90:386–391

    Article  CAS  Google Scholar 

  17. Tong T, Ondov JM, Buchholz BA, Vanderveer MC (2016) Contemporary carbon content of bis (2-ethylhexyl) phthalate in butter. Food Chem 190:1064–1068

    Article  CAS  PubMed  Google Scholar 

  18. Wang B, Wang H, Zhou W, Chen Y, Zhou Y, Jiang Q (2015) Urinary excretion of phthalate metabolites in school children of china: implication for cumulative risk assessment of phthalate exposure. Environ Sci Technol 49:1120–1129

    Article  CAS  PubMed  Google Scholar 

  19. Chiellini F, Ferri M, Morelli A, Dipaola L, Latini G (2013) Perspectives on alternatives to phthalate plasticized poly(vinyl chloride) in medical devices applications. Prog Polym Sci 38:1067–1088

    Article  CAS  Google Scholar 

  20. Choi J, Kwak S (2007) Hyperbranched poly(ε-caprolactone) as a nonmigrating alternative plasticizer for phthalates in flexible PVC. Environ Sci Technol 41:3763–3768

    Article  CAS  PubMed  Google Scholar 

  21. Choi W, Chung JW, Kwak S (2014) Unentangled Star-Shape poly(ε-caprolactone)s as phthalate-free PVC plasticizers designed for non-toxicity and improved migration resistance. ACS Appl Mater Int 6:11118–11128

    Article  CAS  Google Scholar 

  22. Meyers DB, Autian J, Guess WL (1964) Toxicity of plastics used in medical practice II: toxicity of citric acid esters used as plasticizers. J Pharm Sci USA 53:774–777

    Article  CAS  Google Scholar 

  23. Finkelstein M, Gold H (1959) Toxicology of the citric acid esters—tributyl citrate, acetyl tributyl citrate, triethyl citrate, and acetyl triethyl citrate. Toxicol Appl Pharm 1:283–298

    Article  CAS  Google Scholar 

  24. Tsumura Y, Ishimitsu S, Kaihara A, Yoshii K, Tonogai Y (2002) Phthalates, adipates, citrate and some of the other plasticizers detected in Japanese retail foods: A survey. J Health Sci 48:493–502

    Article  CAS  Google Scholar 

  25. Andrade AJM, Grande SW, Talsness CE, Gericke C, Grote K, Golombiewski A, Sterner-Kock A, Chahoud I (2006) A dose response study following in utero and lactational exposure to di-(2-ethylhexyl) phthalate (DEHP): reproductive effects on adult male offspring rats. Toxicology 228:85–97

    Article  CAS  PubMed  Google Scholar 

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

    Article  CAS  Google Scholar 

  27. Chen J, Liu Z, Li X, Liu P, Jiang J, Nie X (2016) Thermal behavior of epoxidized cardanol diethyl phosphate as novel renewable plasticizer for poly(vinyl chloride). Polym Degrad Stabil 126:58–64

    Article  CAS  Google Scholar 

  28. Ye J, Liu S, Xiang J, Lei J, Zhou C (2013) Preparation and application of triglyceride plasticizers for poly(vinyl chloride). J Appl Polym Sci 129:1915–1921

    Article  CAS  Google Scholar 

  29. Benaniba MT, Massardier-Nageotte V (2010) Evaluation effects of biobased plasticizer on the thermal, mechanical, dynamical mechanical properties, and permanence of plasticized PVC. J Appl Polym Sci 118:3499–3508

    Article  CAS  Google Scholar 

  30. Van Krevelen DW, Te Nijenhuis K (2009) Properties of polymers. Elsevier, Amsterdam

    Book  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (NO. 51603132). The authors are grateful to the “Taishan” project supported by Shandong province.

Author information

Author notes

    Authors and Affiliations

    1. State Key Laboratory of Polymer Materials and Engineering, Polymer Research Institute of Sichuan University, Chengdu, 610065, China

      Yanjun Wang, Changlin Zhou, Yao Xiao, Chune Wang, Xiaofeng Chen, Kai Hu, Xiaowei Fu & Jingxin Lei

    2. College of Materials and Chemistry and Chemical Engineering, Chengdu University of Technology, Chengdu, 610059, China

      Shiyi Zhou

    Authors
    1. Yanjun Wang
      View author publications

      You can also search for this author in PubMed Google Scholar

    2. Changlin Zhou
      View author publications

      You can also search for this author in PubMed Google Scholar

    3. Yao Xiao
      View author publications

      You can also search for this author in PubMed Google Scholar

    4. Shiyi Zhou
      View author publications

      You can also search for this author in PubMed Google Scholar

    5. Chune Wang
      View author publications

      You can also search for this author in PubMed Google Scholar

    6. Xiaofeng Chen
      View author publications

      You can also search for this author in PubMed Google Scholar

    7. Kai Hu
      View author publications

      You can also search for this author in PubMed Google Scholar

    8. Xiaowei Fu
      View author publications

      You can also search for this author in PubMed Google Scholar

    9. Jingxin Lei
      View author publications

      You can also search for this author in PubMed Google Scholar

    Corresponding author

    Correspondence to Changlin Zhou.

    Rights and permissions

    Reprints and permissions

    About this article

    Check for updates. Verify currency and authenticity via CrossMark

    Cite this article

    Wang, Y., Zhou, C., Xiao, Y. et al. Preparation and evaluation of acetylated mixture of citrate ester plasticizers for poly(vinyl chloride). Iran Polym J 27, 423–432 (2018). https://doi.org/10.1007/s13726-018-0620-y

    Download citation

    • Received:

    • Accepted:

    • Published:

    • Issue Date:

    • DOI: https://doi.org/10.1007/s13726-018-0620-y

    Keywords

    Search

    Navigation