Abstract
Poly(vinyl chloride) (PVC), plasticized by di(2-ethylhexyl) phthalate (DEHP), medium molecular mass polyesterurethane (PU) or by both plasticizers, was thermally degraded under dynamic thermogravimetric conditions and the kinetics of decomposition was studied by isoconversional methods and by non-linear regression. It has been found that the initial decomposition temperature is higher for PVC plasticized with PU, as compared with PVC plasticized with di(2-ethylhexyl) phthalate (DEHP) or plasticized with PU/DEHP, and thermal degradation shows features of a multi-step complex process. Application of polymeric plasticizer leads to the increase and a 'smoothing' effect in the course of energy of activation and pre-exponential factor at the initial stage of decomposition indicating thus the hindered migration of medium molecular mass compound from PVC matrix (in comparison with PVC containing monomeric DEHP) due to steric hindrances as well as due to specific interactions between C=O and Cl groups along the macrochains. Kinetic model function of the decomposition process of PVC/DEHP and PVC/DEHP/PU blends was found to be a two-stage autocatalyzed reaction of nth order; autocatalytic effect is associated most likely with the role of HCl formed during PVC decomposition. For PVC/PU blend best fit was found by non-linear regression for a two-stage scheme in which first stage was Prout-Tompkins model and the second was autocatalytical model of nth order - the first one involves particle disintegration, which was promoted by product generation at branching PVC 'pseudo-crystals' nuclei, thus exposing more surface on which decomposition reaction proceeds.
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References
B Schneider J Schena R Truog M Jacobson S Kevy (1989) N. Engl. J. Med. 320 1563
S Lakshmi A Jayakrishnan (1998) Polymer 39 151 Occurrence Handle10.1016/S0032-3861(97)00244-9 Occurrence Handle1:CAS:528:DyaK2sXnslWntro%3D
AO Earls IP Axford JH Braybrook (2003) J. Chromat. A 983 237 Occurrence Handle1:CAS:528:DC%2BD38XpsFejt7Y%3D
EJ Wickson (Eds) (1993) Handbook of PVC Formulating Wiley New York
F Xiao L Shi M Xy (1991) Polym. Degr. Stab. 31 51 Occurrence Handle10.1016/0141-3910(91)90095-9 Occurrence Handle1:CAS:528:DyaK3MXisFSnsw%3D%3D
E Corradini A Forti E Curti (1997) Eur. Polym. J. 33 1651 Occurrence Handle1:CAS:528:DyaK1cXntF2ktA%3D%3D
JR Pena M Hidalgo C Mijangos (2000) J. Appl. Polym. Sci. 75 1303 Occurrence Handle1:CAS:528:DC%2BD3cXmvFOntQ%3D%3D
A Jimenez L Torre JM Kenny (2001) Polym. Degrad. Stab. 73 447 Occurrence Handle1:CAS:528:DC%2BD3MXmt12it70%3D
T Kovacic Z Mrklic (2002) Thermochim. Acta 381 49 Occurrence Handle10.1016/S0040-6031(01)00643-8 Occurrence Handle1:CAS:528:DC%2BD3MXptFGqu78%3D
B Świerz-Motysia J Kozakiewicz J Przybylski J Pełka (1999) Polimery 44 780
Polish patent appl., 339505 (2000).
B Świerz-Motysia (2001) Annual Report'2001 Industrial Chemistry Research Institute Warsaw 72
B Świerz-Motysia K Pielichowski (2005) Polimery 50 601
T Ozawa (1965) Bull. Chem. Soc. Jpn. 38 1881 Occurrence Handle1:CAS:528:DyaF28XjtVyisQ%3D%3D
JH Flynn LA Wall (1966) Polym. Lett. 4 232 Occurrence Handle10.1002/pol.1966.110040504
HL Friedman (1965) J. Polym. Sci. C6 175
JJ Pysiak YA Al-Baldwi (2004) J. Therm. Anal. Cal. 76 521 Occurrence Handle10.1023/B:JTAN.0000028029.97849.87 Occurrence Handle1:CAS:528:DC%2BD2cXktVWhtbc%3D
P Šimon (2004) J. Therm. Anal. Cal. 76 123
A Murase M Sugiura T Araga (1994) Polym. Degrad. Stab. 43 415 Occurrence Handle1:CAS:528:DyaK2cXislajs74%3D
L Audouin B Dalle G Metzger J Verdu (1992) J. Appl. Polym. Sci. 45 2091 Occurrence Handle1:CAS:528:DyaK38Xltlais7Y%3D
P Dunn BC Ennis (1970) J. Appl. Polym. Sci. 14 355 Occurrence Handle1:CAS:528:DyaE3cXnvFOnsg%3D%3D
A Jimenez V Berenguer J Lopez J Vilaplana (1996) J. Appl. Polym. Sci. 60 2041 Occurrence Handle10.1002/(SICI)1097-4628(19960620)60:12<2041::AID-APP1>3.0.CO;2-M Occurrence Handle1:CAS:528:DyaK28Xjt1SisrY%3D
A Marcilla M Beltran (1996) Polym. Degrad. Stab. 53 251 Occurrence Handle1:CAS:528:DyaK28XlvFagurk%3D
KB Abbas EM Sorvik (1976) J. Appl. Polym. Sci. 20 2395 Occurrence Handle1:CAS:528:DyaE28Xlt1Cmu78%3D
K Pielichowski J Pielichowski K German (1995) Polimery 5 257
K Pielichowski J Pielichowski K German (1995) Polimery 6 317
M Benes N Milanov G Matuschek A Kettrup V Placek V Balek (2004) J. Therm. Anal. Cal. 78 621 Occurrence Handle1:CAS:528:DC%2BD2cXovFOgtrk%3D
R Bacaloglu M Fisch (1995) Polym. Degrad. Stab. 47 33 Occurrence Handle1:CAS:528:DyaK2MXkt1Gjt74%3D
JY Moisan (1980) Eur. Polym. J. 16 979 Occurrence Handle1:CAS:528:DyaL3MXkvVajsw%3D%3D
W Barendswaard VM Litvinov F Souren RL Scherrenberg C Gondard C Colemonts (1999) Macromolecules 32 167 Occurrence Handle10.1021/ma971508y Occurrence Handle1:CAS:528:DyaK1cXotVSrs78%3D
RL Scherrenberg H Reynaers K Mortnesen W Vlak C Gondard (1993) Macromolecules 26 3205 Occurrence Handle1:CAS:528:DyaK3sXisFGru7c%3D
B Garnaik S Sivaram (1996) Macromolecules 29 185 Occurrence Handle10.1021/ma951086x Occurrence Handle1:CAS:528:DyaK2MXpvVeitL4%3D
LY Chenborisova VS Ionkin AI Maklakov VA Voskresenskii (1966) Vysokomol. Soedin. 8 1810 Occurrence Handle1:CAS:528:DyaF2sXivFCrsw%3D%3D
CJ Singleton T Stephenson J Isner PH Geil EA Collins (1977) J. Macromol. Sci., Phys. B14 29 Occurrence Handle1:CAS:528:DyaE2sXltlKktr8%3D
EG Prout FC Tompkins (1944) Trans. Faraday Soc. 40 488 Occurrence Handle10.1039/tf9444000488 Occurrence Handle1:CAS:528:DyaH2MXhsVCrsw%3D%3D
R.L Scherrenberg H Reynaers C Gondard PAM Steeman (1994) J. Polym. Sci., Polym. Phys. 32 111 Occurrence Handle1:CAS:528:DyaK2cXhtVyiurs%3D
A Gray M Gilbert (1976) Polymer 17 44 Occurrence Handle10.1016/0032-3861(76)90152-X Occurrence Handle1:CAS:528:DyaE28XktVKhsro%3D
CE Scott CW Macosco (1995) Polymer 36 461 Occurrence Handle10.1016/0032-3861(95)91554-K Occurrence Handle1:CAS:528:DyaK2MXjvVymtbo%3D
SY Kwak N Nakayima (1996) Macromolecules 29 5446 Occurrence Handle1:CAS:528:DyaK28XktVWktLo%3D
SJ Guerrero (1989) Macromolecules 22 3480 Occurrence Handle10.1021/ma00198a046 Occurrence Handle1:CAS:528:DyaL1MXkvFyhsbY%3D
DJM Clark RW Truss (1996) J. Polym. Sci., Part B: Polym. Phys. 34 103 Occurrence Handle10.1002/(SICI)1099-0488(19960115)34:1<103::AID-POLB8>3.0.CO;2-Y Occurrence Handle1:CAS:528:DyaK28XhtVGhtQ%3D%3D
M Gilbert J Macromol (1994) Sci. Rev. Macromol. Chem. Phys. C34 77 Occurrence Handle1:CAS:528:DyaK2cXjtFKgtQ%3D%3D
RJ Hobson AH Windle (1993) Macromol. Chem.,Theory Simul. 2 257 Occurrence Handle1:CAS:528:DyaK3sXhsVygtrc%3D
A Elicegui JJ Del Val V Bellenger J Verdu (1997) Polymer 38 1647 Occurrence Handle10.1016/S0032-3861(96)00671-4 Occurrence Handle1:CAS:528:DyaK2sXitFanu74%3D
JJ Ziska DR Paul (1981) Polymer 22 918 Occurrence Handle10.1016/0032-3861(81)90268-8 Occurrence Handle1:CAS:528:DyaL38Xjs1Witg%3D%3D
A Koscielecka (1993) Eur. Polym. J. 29 23 Occurrence Handle1:CAS:528:DyaK3sXktVSlsQ%3D%3D
D Allard RE Prud'homme (1982) J. Appl. Polym. Sci. 27 559 Occurrence Handle10.1002/app.1982.070270219 Occurrence Handle1:CAS:528:DyaL38XhvVWqtbY%3D
M Aubin Y Bedard MF Morrissette RE Prud'homme (1983) J. Polym. Sci., Polym. Phys. Edn. 21 233 Occurrence Handle1:CAS:528:DyaL3sXht1Kqt7c%3D
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Pielichowski, K., Świerz-Motysia, B. Influence of polyesterurethane plasticizer on the kinetics of poly(vinyl chloride) decomposition process . J Therm Anal Calorim 83, 207–212 (2006). https://doi.org/10.1007/s10973-005-7007-y
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DOI: https://doi.org/10.1007/s10973-005-7007-y