Polyvinyl chloride (PVC) films containing the mercaptan methyltin (S), zinc stearate (Z) and dipentaerythritol (D) additives were prepared. The thermal degradation kinetics of the films were investigated by nonisothermal thermogravimetry and TG–FTIR techniques. Using the nonmodel method and the Kissinger, the Friedman, the Kissinger–Akahira–Sunose and the Flynn–Wall–Ozawa methods, the average apparent activation energies of the PVC–SZD films in the first and second thermal decomposition stages obtained were 127.5 and 261.6 kJ mol−1, respectively. Compared with the experimental master plot by the generalized master plot, the experimental and theoretical master plots on the master plot of θ/θ0.5 versus α show that the thermal degradation of PVC-SZD film conforms to the chemical reaction F1.5 mechanism model. TG–FTIR analysis showed that the infrared vibration peaks ordered from strong to weak after adding SZD components were: νCO2 (638 °C) > ν(–COOR) (275 °C) > νHCl (299 °C). The thermal degradation of the film did not show hydroxyl or moisture formation compared to the blank. The removal of carboxyl groups of plasticizer dioctyl terephthalate (DOTP) in PVC was significantly inhibited, and the CO2 gas released by thermal degradation was reduced by 85.2%. This suggests that SZD has a strong interaction with the ester groups in DOTP, and there is the possibility of generating a more stable carboxyl group-containing metal complex, which creates favorable conditions for the recovery of DOTP. When the heating rates were 2.5, 5.0, 10 and 20 °C min−1, the lowest temperatures at which the conversions reached 5 and 10% were 226.1 °C and 239.1 °C, respectively.
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Hahladakis JN, Velis CA, Weber R, Iacovidou E, Purnell P. An overview of chemical additives present in plastics: migration, release, fate and environmental impact during their use, disposal and recycling. J Hazard Mater. 2018;344:179–99.
Yu J, Sun LS, Ma C, Qiao Y, Yao H. Thermal degradation of PVC: a review. Waste Manag. 2016;48:300–14.
Castro A, Soares D, Vilarinho C. Kinetics of thermal de-chlorination of PVC under pyrolytic conditions. Waste Manag. 2012;32:847–51.
Zhu HM, Jiang XG, Yan JH, Chi Y, Cen KF. TG–FTIR analysis of PVC thermal degradation and HCl removal. J Anal Appl Pyrol. 2008;82:1–9.
Xu FF, Wang B, Yang D, Hao JH, Qiao YY, Tian YY. Thermal degradation of typical plastics under high heating rate conditions by TG–FTIR: pyrolysis behaviors and kinetic analysis. Energy Convers Manag. 2018;171:1106–15.
Cao QM, Yuan GA, Yin LJ, Chen DZ, He PJ, Wang H. Morphological characteristics of polyvinyl chloride (PVC) dechlorination during pyrolysis process: influence of PVC content and heating rate. Waste Manag. 2016;58:241–9.
Honus S, Kumagai S, Fedorko G, Molnár V, Yoshioka T. Pyrolysis gases produced from individual and mixed PE, PP, PS, PVC, and PET—part I: production and physical properties. Fuel. 2018;221:346–60.
Sadat-Shojai M, Bakhshandeh GR. Recycling of PVC wastes. Polym Degrad Stab. 2011;96:404–15.
Wu JL, Chen TJ, Luo XT, Han DZ, Wang ZQ, Wu JH. TG/FTIR analysis on co-pyrolysis behavior of PE, PVC and PS. Waste Manag. 2014;34:676–82.
Beneš M, Milanov N, Matuschek G, Kettrup A, Plaček V, Balek V. Thermal degradation of PVC cable insulation studied by simultaneous TG–FTIR and TG–EGA methods. J Therm Anal Calorim. 2004;78:621–30.
Jackić M, Vrandečić NS, Erceg M. Kinetic analysis of the non-isothermal degradation of poly(vinyl chloride)/poly(ethylene oxide) blends. J Therm Anal Calorim. 2016;123:1513–22.
Krongauz VV, Lee YP, Bourassa A. Kinetics of thermal degradation of poly(vinyl chloride). J Therm Anal Calorim. 2011;106:139–49.
Beneš M, Plaček V, Matuschek G, Kettrup AA, Györyová K, Emmerich WD, Balek V. Lifetime simulation and thermal characterization of PVC cable insulation materials. J Therm Anal Calorim. 2005;82:761–8.
Sánchez-Jiménez PE, Perejón A, Criado JM, Diánez MJ, Pérez-Maqueda LA. Kinetic model for thermal dehydrochlorination of poly(vinyl chloride). Polymer. 2010;51:3998–4007.
Wang YL, Wang XY, Liu LM, Peng XY. Theoretical study on the thermal dehydrochlorination of model compounds for poly(vinyl chloride). J Mol Struct Theochem. 2009;896:34–7.
Ludwig V, Da Costaludwig ZM, Rodrigues MM, Anjos V, Costa CB, Sant’ Anna das Dores DR, da Silva VR, Soares F. Analysis by Raman and infrared spectroscopy combined with theoretical studies on the identification of plasticizer in PVC films. Vib Spectrosc. 2018;98:134–8.
Fang YQ, Wang QW, Guo CG, Song YM, Cooper PA. Effect of zinc borate and wood flour on thermal degradation and fire retardancy of Polyvinyl chloride (PVC) composites. J Anal Appl Pyrol. 2013;100:230–6.
Mohamed NA. Biologically active maleimido aromatic 1,3,4-oxadiazole derivatives evaluated thermogravimetrically as stabilizers for rigid PVC. J Therm Anal Calorim. 2018;131:2535–46.
Wang CJ, Liu HR, Zhang JQ, Yang SL, Zhang Z, Zhao WP. Thermal degradation of flame-retarded high-voltage cable sheath and insulation via TG–FTIR. J Anal Appl Pyrol. 2018;134:167–75.
Lu YH, Liu WL, Wei F, Ma SC. Effect of barium stearate on the thermal stability of polyvinyl chloride. Appl Mech Mater. 2013;395–396:371–6.
Wei F, Lu YH, Liu WL. Effect of organotin on the thermal stability of poly(vinyl chloride). Adv Mater Res. 2012;550–553:838–42.
Vyazovkin S, Burnham AK, Criado JM, Pérez-Maqueda LA, Popescu C, Sbirrazzuoli N. ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data. Thermochim Acta. 2011;520(1–2):1–19.
Kissinger HE. Reaction kinetics in differential thermal analysis. Anal Chem. 1957;29(11):1702–6.
Ozawa T. A new method of analyzing thermogravimetric data. Bull Chem Soc Jpn. 1965;38(11):1881–6.
Flynn JH, Wall LA. General treatment of the thermogravimetry of polymers. J Res Natl Bur Stand. 1966;70(6):487–523.
Friedman HL. Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to a phenolic plastic. J Polym Sci Polym Symp. 1964;6(1):183–95.
Akahira T, Sunose T. Method of determining activation deterioration constant of electrical insulating materials. Res Rep Chiba Inst Technol (Sci Technol). 1971;16:22–31.
Gotor FJ, Criado JM, Malek J, Koga N. Kinetic analysis of solid-state reactions: the universality of master plots for analyzing isothermal and nonisothermal experiments. J Phys Chem A. 2000;104(46):10777–82.
Sánchez-Jiménez PE, Pérez-Maqueda LA, Perejón A, Criado JM. Generalized master plots as a straightforward approach for determining the kinetic model: the case of cellulose pyrolysis. Thermochim Acta. 2013;552:54–9.
Turmanova SC, Genieva SD, Dimitrova AS, Vlaev LT. Non-isothermal degradation kinetics of filled with rise husk ash polypropene composites. Express Polym Lett. 2008;2(2):133–46.
Senum GI, Yang RT. Rational approximations of the integral of the Arrhenius function. J Therm Anal. 1977;11:445.
Flynn JH. The ‘temperature integral’-its use and abuse. Thermochim Acta. 1997;300:83–92.
Fazekas P, Czégény Z, Mink J, Bódis E, Klébert S, Németh C, Keszler AM, Károly Z, Szépvölgyi J. Decomposition of poly(vinyl chloride) in inductively coupled radiofrequency thermal plasma. Chem Eng J. 2016;302:163–71.
Jia PY, Hu LH, Zhang M, Zhou YH. TG–FTIR and TG–MS analysis applied to study the flame retardancy of PVC–castor oil-based chlorinated phosphate ester blends. J Therm Anal Calorim. 2016;124:1331–9.
Qi YX, Wu WH, Han LJ, Qu HQ, Han X, Wang AQ, Xu JZ. Using TG–FTIR and XPS to understand thermal degradation and flame-retardant mechanism of flexible poly(vinyl chloride) filled with metallic ferrites. J Therm Anal Calorim. 2016;123:1263–71.
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Xue, M., Lu, Y., Li, K. et al. Thermal characterization and kinetic analysis of polyvinyl chloride containing Sn and Zn. J Therm Anal Calorim 139, 1479–1492 (2020). https://doi.org/10.1007/s10973-019-08505-0
- Methyltin mercaptan
- Thermal degradation kinetics