Skip to main content
SpringerLink
Log in

Evaluation of the thermal stabilization behavior of hydrotalcite against organic stabilizers for plasticized PVC films

  • Original Paper
  • Published:
Polymer Bulletin Aims and scope Submit manuscript

Abstract

This study focuses on the systematic comparison of the thermal stabilization behavior of the hydrotalcite which is present in the nature and is non-toxic, with organic stabilizers (mixed metal salts, maleimide and tri-nonyl phenyl phosphite) having high stabilizing efficiency. For the purpose of this study, first plastisols were prepared by mixing plasticizer and thermal stabilizers into the PVC resin. Then films were obtained from plastisols, which were applied on a glass plate as 150μ thick films with the help of a film applicator. The films were cured for 15 min in oven at 160 °C to produce plastigel films. The stabilization behavior of these films was measured by applying various stabilization testing methods: thermal aging test, oxidation index, polyene formation measurement and discoloration. Thermal aging studies for these plastigel films were carried out at 100 and 150 °C up to 420 min. Oxidation index values are associated with oxidized surface layer that is formed after the aging and degradation of the films, which are determined by FTIR spectroscopy. Thermal stability behavior in terms of concentration of polyenes formed due to the released HCl has been investigated by UV–visible spectroscopy. Color changes of the degraded films were followed by observed colorimetry. According to the results, number of the polyenes for all degraded films increased with increasing time and temperature. The results have proved the greater stabilizing efficiency of hydrotalcite relative to that of the thermal stabilizers in terms of the number of the conjugated double bond, polyene concentration, polyene formation rate and change in color. It is believed that the results will contribute to the thermal stability of PVC by different stabilizers and blends, and an effort has been made in this article to throw light on this issue.

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

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12

Similar content being viewed by others

References

  1. Folarin OM, Sadiku ER (2011) Thermal stabilizers for poly(vinyl chloride): a review. Int J Phys Sci 6(18):4323–4330

    Google Scholar 

  2. Tüzüm Demir AP, Ulutan S (2015) Degradation kinetics of PVC plasticized with different plasticizers under isothermal conditions. J Appl Polym Sci 132:41579. https://doi.org/10.1002/app.41579

    Article  CAS  Google Scholar 

  3. Wen R, Yang Z, Chen H, Hu Y, Duan J (2012) Zn–Al–La hydrotalcite-like compounds as heating stabilizer in PVC resin. J Rare Earths 30(9):895–902

    CAS  Google Scholar 

  4. Babinsky R (2007) PVC additives—a global review. J Vinyl Addit Technol. https://doi.org/10.1002/vnl.20099

    Article  Google Scholar 

  5. Vieira MGA, Silva MA, Santos LO, Beppu MM (2011) Natural-based plasticizers and biopolymer films: a review. Eur Polym J 47(3):254–263

    CAS  Google Scholar 

  6. Egbuchunam TO, Balköse D, Okieimen FE (2007) Effect of zinc soaps of rubber seed oil (RSO) and/or epoxidised rubber seed oil (ERSO) on the thermal stability of PVC plastigels. Polym Degrad Stab 92:1572–1582

    CAS  Google Scholar 

  7. Sabaa MW, Mohamed RR, Yassin AA (2003) Organic thermal stabilizers for rigid poly(vinyl chloride) VIII. Phenylurea and phenylthiourea derivatives. Polym Degrad Stab 81(1):37–45

    CAS  Google Scholar 

  8. Benaniba MT, Belhaneche-Bensemra N, Gelbard G (2003) Stabilization of PVC by epoxidized sunflower oil in the presence of zinc and calcium stearates. Polym Degrad Stab 82:245–249

    CAS  Google Scholar 

  9. Sánchez-Jiménez PE, Perejón A, Criado JM, Diánez MJ, Pérez-Maqueda LA (2010) Kinetic model for thermal dehydrochlorination of poly(vinyl chloride). Polymer 51:3998–4007

    Google Scholar 

  10. Mohammed FS, Conley M, Rumple AC, Saunders SR, Switzer J, Urena-Benavides E, Jha R, Cogen JM, Chaudhary BI, Pollet P, Eckert CA, Liotta CL (2015) Enhanced thermal stabilization and reduced color formation of plasticized poly(vinyl chloride) using zinc and calcium salts of 11-maleimideoundecanoic acid. Polym Degrad Stab 111:64–70

    CAS  Google Scholar 

  11. Xu X, Chen S, Tang W, Qu Y, Wang X (2014) Investigation of basic zinc cyanurate as a novel thermal stabilizer for poly(vinyl chloride) and its synergistic effect with calcium stearate. Polym Degrad Stab 99:211–218

    CAS  Google Scholar 

  12. Atakul Savrık S, Balköse D, Ulutan S, Ülkü S (2010) Characterization of poly(vinyl chloride) powder produced by emulsion polymerization. J Therm Anal Calorim 101:801–806

    Google Scholar 

  13. Ureta E, Cantú ME (2000) Zinc maleate and zinc anthranilate as thermal stabilizers for PVC. J Appl Polym Sci 77:2603–2605

    CAS  Google Scholar 

  14. Zweifel H (2000) Plastics additives handbook, 5th edn. Hanser Verlag, Munich

    Google Scholar 

  15. Semsarzadeh MA, Mehrabzadeh M, Arabshahi SS (2002) Dynamic mechanical behavior of the dioctyl phthalate plasticized polyvinyl chloride–epoxidized soya bean oil. Eur Polym J 38:351–358

    CAS  Google Scholar 

  16. Xu X, Chen S, Tang W, Qu Y, Wang X (2013) Synthesis and application of uracil derivatives as novel thermal stabilizers for rigid poly(vinyl chloride). Polym Degrad Stab 98:659–665

    CAS  Google Scholar 

  17. Liu J, Chen G, Yang J (2008) Preparation and characterization of poly(vinyl chloride)/layered double hydroxide nanocomposites with enhanced thermal stability. Polymer 49(18):3923–3927

    CAS  Google Scholar 

  18. Tüzüm-Demir AP, Ulutan S (2018) Assessment of degradation of plasticized poly(vinyl chloride) films through polyene formation under isothermal conditions. J Appl Polym Sci 135:46092

    Google Scholar 

  19. Van der Ven L, Van Gemert MLM, Batenburg LF, Keern JJ, Gielgens LH, Koster TPM, Fischer HR (2000) On the action of hydrotalcite-like clay materials as stabilizers in polyvinylchloride. Appl Clay Sci 17:25–34

    Google Scholar 

  20. Mohamed NA, Abd El-Ghany NA, Fahmy MM, Ahmed MH (2015) Synergistic effect of maleimido phenyl urea derivatives mixed with some commercial stabilizers on the efficiency of thermal stabilization of PVC. Polym Test 44:66–71

    CAS  Google Scholar 

  21. Ratnam CT, Zaman K (1999) Enhancement of polyvinyl chloride (PVC)/epoxidised natural rubber (ENR) blend properties by electron beam irradiation: effect of antioxidants. Polym Degrad Stab 65:481–490

    CAS  Google Scholar 

  22. Fahmy MM (2010) Inhibition of the thermal degradation of rigid poly(vinyl chloride) using poly(N-[4-(N0-phenyl amino carbonyl)phenyl]maleimide). J Appl Polym Sci 115:2013–2018

    CAS  Google Scholar 

  23. Stevenson DR, Jennings TC, Harr ME, Jakupca MR (2004) Phosphite ester additive composition, United States Patent US 6,824,711 B2

  24. Keeney CN (1979) Effect of phosphate esters on PVC flammability from a multi-test viewpoint. Vinyl Addit Technol. https://doi.org/10.1002/vnl.730010315

    Article  Google Scholar 

  25. Levchic SV, Weil ED (2005) Review overview of the recent literature on flame retardancy and smoke suppression in PVC. Polym Adv Technol 16:707–716

    Google Scholar 

  26. Sabaa MW, Mikhael MG, Mohamed NA, Yassin AA (1990) N-substituted maleimides as thermal stabilizers for plasticized poly(vinyl chloride). Polym Degrad Stab 27(3):319–336

    CAS  Google Scholar 

  27. Gupta S, Agarwal DD, Banerjee S (2009) Thermal stabilization of poly(vinyl chloride) by hydrotalcites, zeolites, and conventional stabilizers. J Vinyl Addit Technol. https://doi.org/10.1002/vnl.20196

    Article  Google Scholar 

  28. Tong M, Chen H, Yang Z, Wen R (2011) The effect of Zn–Al–hydrotalcites composited with calcium stearate and β-diketone on the thermal stability of PVC. Int J Mol Sci 12:1756–1766. https://doi.org/10.3390/ijms12031756

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  29. Darder M, López-Blanco M, Aranda P, Leroux F, Ruiz-Hitzky E (2005) Bio-nanocomposites based on layered double hydroxides. Chem Mater 17:1969–1977

    CAS  Google Scholar 

  30. Wang X, Zhang Q (2004) Effect of hydrotalcite on the thermal stability, mechanical properties, rheology and flame retardance of poly(vinyl chloride). Polym Int 53:698–707

    CAS  Google Scholar 

  31. Molefe DM, Labuschagne J, Focke WW, Westhuizen I, Ofosu O (2015) The effect of magnesium hydroxide, hydromagnesite and layered double hydroxide on the heat stability and fire performance of plasticized poly(vinyl chloride). J Fire Sci 33(6):493–510

    CAS  Google Scholar 

  32. Runjuan W, Zhanhong Y, Hongyan C, Youwang H, Ji’an D (2012) Zn–Al–La hydrotalcite-like compounds as heating stabilizer in PVC resin. J Rare Earths 30(9):895

    Google Scholar 

  33. Mane SM, Thorat BN, Sawant MR (2012) Synthesis and characterization of tris (nonyl) phenyl phosphite and interfacial study with Karanja oil in acetonitrile solution. J Dispers Sci Technol 33(3):357–361. https://doi.org/10.1080/01932691.2011.567150

    Article  CAS  Google Scholar 

  34. Boughattas I, Ferry M, Dauvois V, Lamouroux C, Dannoux-Papin A, Leonie E, Balanzat E, Esnouf S (2016) Thermal degradation of γ-irradiated PVC: I-dynamical experiments. Polym Degrad Stab 126:219–226

    CAS  Google Scholar 

  35. Benavides R, Castillo BM, Castañeda AO, López GM, Arias G (2001) Different thermo-oxidative degradation routes in poly(vinyl chloride). Polym Degrad Stab 73(3):417–423

    CAS  Google Scholar 

  36. Arkıs E, Balköse D (2005) Thermal stabilisation of poly(vinyl chloride) by organotin compounds. Polym Degrad Stab 88:46–51

    Google Scholar 

  37. Li M, Zhang J, Xin J, Huang K, Li S, Wang M, Xia J (2017) Design of green zinc-based thermal stabilizers derived from tung oil fatty acid and study of thermal stabilization for PVC. J Appl Polym Sci. https://doi.org/10.1002/APP.44679

    Article  Google Scholar 

  38. Li M, Zhang J, Huang K, Li S, Jiang J, Xia J (2014) Mixed calcium and zinc salts of dicarboxylic acids derived from rosin and dipentene: preparation and thermal stabilization for PVC. RSC Adv 4:63576

    CAS  Google Scholar 

  39. Lin YJ, Li DQ, Evans DG, Duan X (2005) Modulating effect of MgeAleCO3 layered double hydroxides on the thermal stability of PVC resin. Polym Degrad Stab 88:286e293

    Google Scholar 

  40. Lin Y, Wang J, Evans DG, Li D (2006) Layered and intercalated hydrotalcite-like materials as thermal stabilizers in PVC resin. J Phys Chem Solids 67:998–1001

    CAS  Google Scholar 

  41. Gupta S, Agarwal DD, Banerjee S (2012) Role of hydrotalcites cations in thermal stabilization of poly (vinyl chloride). Int J Polym Mater 61(2):124–135. https://doi.org/10.1080/00914037.2011.574657

    Article  CAS  Google Scholar 

  42. Xue X, Zhang H, Zhang S (2014) Preparation of MgAl LDHs intercalated with amines and effect on thermal behavior for poly(vinyl chloride). Adv Mater Phys Chem 4:258–266

    Google Scholar 

  43. Zhang Q, Li H (2008) Investigation on the thermal stability of PVC filled with hydrotalcite by the UV–Vis spectroscopy. Spectrochim Acta A 69:62–64

    Google Scholar 

  44. Gupta S, Agarwal DD, Banerjee S (2008) Synthesis and characterization of hydrotalcites: potential thermal stabilizers for PVC. Indian J Chem 47A:1004–1008

    CAS  Google Scholar 

  45. Burgos N, Jiménez A (2009) Degradation of poly(vinyl chloride) plasticized with non-phthalate plasticizers under sterilization conditions. Polym Degrad Stab 94:1473–1478

    CAS  Google Scholar 

  46. Manzoor W, Yousaf SM, Ahmad Z (1996) Degradation of PVC: effect of zinc chloride on the concentration of polyenes. Polym Degrad Stab 51:295–299

    CAS  Google Scholar 

  47. Baltacıoğlu H, Balköse D (1999) Effect of zinc stearate and/or epoxidized soybean oil on gelation and thermal stability of PVC-DOP plastigels. J Appl Polym Sci 74:2488–2498

    Google Scholar 

  48. Castañeda-Facio A, Benavides R, Martınez-Pardo ME (2014) Thermal stability of PVC formulations gamma irradiated at different dose rates. Radiat Phys Chem 97:75

    Google Scholar 

  49. Tüzüm-Demir AP, Ulutan S (2013) Migration of phthalate and non-phthalate plasticizers out of plasticized PVC films into air. J Appl Polym Sci 128:1948–1961

    Google Scholar 

  50. Paul H, Daniel A (2009) brief overview of theories of PVC plasticization and methods used to evaluate PVC-plasticizer interaction. J Vinyl Addit Technol 15(4):219–223

    Google Scholar 

  51. Ulutan S (2003) Influence of additional thermal stabilizers on the reprocessing of postconsumer poly(vinyl chloride) bottles. J Appl Polym Sci 90:3994–3999

    CAS  Google Scholar 

  52. Fahmy MM, Mohamed RR, Mohamed NA (2012) Novel antimicrobial organic thermal stabilizer and co-stabilizer for rigid PVC. Molecules 17:7927–7940. https://doi.org/10.3390/molecules17077927

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  53. Gilbert M, Ho KC, Hitt DJ, Vrsaljko D (2013) Assessment of PVC stabilisation using hydrotalcites e Raman spectroscopy and other techniques. Polym Degrad Stab 98:1537–1547

    CAS  Google Scholar 

  54. Najafi V, Ahmadi E, Ziaee F (2018) Chemical modification of PVC by different nucleophiles in solvent/non-solvent system at high temperature. Iran Polym J 27:841–850

    CAS  Google Scholar 

  55. Fu M, Li D, Liu H, Zhang J (2015) Insights into the use of zinc–mannitol alkoxide as a novel thermal stabilizer for rigid poly(vinyl chloride). J Appl Polym Sci. https://doi.org/10.1002/APP.42038

    Article  Google Scholar 

Download references

Acknowledgements

The financial support of Usak University Research Fund (Project No: 2016/TP005- UBAP 06) is gratefully acknowledged, as well. The present study is partially based on the presentation at the 29. National Chemistry Congress, organized by Middle East Technical University, Ankara, Turkey, September 10–14, 2017.

Author information

Authors and Affiliations

  1. Chemical Engineering Department, Faculty of Engineering, Usak University, 64200, Usak, Turkey

    Ç. Korkusuz & A. P. Tüzüm Demir

Authors
  1. Ç. Korkusuz
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. A. P. Tüzüm Demir
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to A. P. Tüzüm Demir.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Korkusuz, Ç., Tüzüm Demir, A.P. Evaluation of the thermal stabilization behavior of hydrotalcite against organic stabilizers for plasticized PVC films. Polym. Bull. 77, 4805–4831 (2020). https://doi.org/10.1007/s00289-019-02977-8

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00289-019-02977-8

Keywords

Search

Navigation