Blazevska-Gilev, D. Spaseska Journal of the University of J.

Chemical Technology and Metallurgy, 45, 3, 2010, 251-254

FORMAL KINETIC ANALYSIS OF PVC THERMAL DEGRADATION

J. Blazevska-Gilev, D. Spaseska

Faculty of Technology and Metallurgy St.Cyril and Methodious University, P.O. Box 580 MK-1001 Skopje, Republic of Macedonia E-mail: jadranka@tmf.ukim.edu.mk

Received 05 April 2010 Accepted 12 June 2010

ABSTRACT This paper presents an initial attempt at describing poly(vinyl chloride) thermal degradation through kinetic model. Non isothermal or dynamic thermogravimetry (TGA) has been used for kinetic study of the thermally activated process of poly(vinyl chloride) (PVC), heating by two different rates up to around 723 K. As the easily measured weight changes of the samples in the defined thermal conditions are a suitable sensor for their structural and chemical changes, by means of some methods like Gropjanov-Abbakumov,s one, the useful information for identifying the formal kinetic parameters of the investigated processes taking place in the course of thermal treatment have been achieved. The thermal variations of the rate constant as well as the kinetic equations for the examined process depending on the investigated parameters have been derived. Keywords: poly(vinyl chloride), thermal degradation, degradation kinetics.

INTRODUCTION Poly(vinyl chloride) (PVC) is commonly used as a thermoplastic because of its wide variability of properties and its application in rigid and soft products [1]. Thermal degradation of PVC is a more complex process than the other stable plastic wastes, i.e. polyethylene (PE), polypropylene (PP) and polystyrene (PS). As a matter of fact, whilst PE, PP and PS thermally react at quite low temperatures, reducing the polymer chain [2,3], PVC pyrolysis involves significant cross-linked reactions with the formation of polyaromatic structures (possibly chlorinated) and a carbonaceous residue (char). Moreover the process description becomes more complex because chlorine needs to be introduced into the system addition to carbon and hydrogen. The literature includes several papers on pyrolysis and gasification of PVC. However some scientists have reviewed the kinetic results of PVC thermal degradation, which have been usually fitted in the literature to a potential kinetic model of the order

d/d = k f() = k0 f() exp(-E/RT). S. Moulay [4] has exposed that PVC degradation takes place in a two steps process, dehydrochlorination and a further degradation step yielding a solid residue and a volatile fraction. In this paper it was derived the analytical shape of the kinetical curves for the two temperature stages of the investigated process by means of GropjanovAbbakumov,s method [5]. EXPERIMENTAL Thermal degradation of poly(vinyl chloride) has been studied during heating up to around 723 K at the rate: dT/d = 4 and 10 o/min using Cahn D-200 recording microbalances in a stream of inert gas at the flow rate 100 ml Ar/min. For the purpose of the identifying the outgoing gases the isothermal analyses were used, subjecting PVC samples 10 min. at the characteristic temperatures. The analysis has been made by automatic sampling gas chromatograph Hewlett-Packard GC

251

Journal of the University of Chemical Technology and Metallurgy, 45, 3, 2010

5890 with FID and TCD detectors and the Porapak P packed column (i.d 2 mm, length 2 m). At the same time the outgoing gas was analyzed continually on mass spectrometer VG GAS Analysis LTD. RESULTS AND DISCUSSION A standard PVC was thermally treated in inert atmosphere, up to 723 K, using a heating rate of 4 and 10 o /min. The thermal degradation occurs in two steps to nearly 89 % weight loss. In Fig.1 the dynamic TG curves of PVC in Ar atmosphere (100) and two different heating rates are presented, but in Fig. 2, the dependences of the degraded sample () on the temperature (T) are shown. The first degradation step lasting up to 573 K, leads to a weight loss of about 65%, but the second one, occurring up to 723 K, results in nearly 85% weight loss as a whole. The liberated gas products as a result of the thermal degradation have been determined by gas chromatography and mass spectrometry. These products are presented in Fig.3 and Fig.4, consequently.

The main gas products released from PVC are methane, ethane, ethyne, hydrogen, HCl, Cl2, 1-butene and benzene, appeared as a result of decomposition and the recombination of the gas products in two steps of the process. The description of the degradation process is difficult, because of the complexity of the chemical reactions carried out at the same time. In this work, the characterization of the rate of weight loss is made by overall kinetic parameters determined on the basis of the weight loss curves. The determination of PVC degradation kinetics is commonly carried out by mathematical treatment of the TG curve, or series of curves obtained under different temperature-ramped conditions. In order to obtain the formal kinetic parameters which explain two steps of the underlying process comprising TG curve, we have adopted GropjanovAbbakumovs method which could analyze groups of reactions in the separated steps, by using two different heating rates. Using the mentioned method, the data of Figs. 1 and 2 as well as the equation d/d = K f() = K0 f() exp(-E/RT)

100 (100-a ), % 80 60 40 20 0 0 200 400 600 4 C/min 10 C/min

where: d/d percentage of the degraded sample in unite time, K0 entropy factor independent on temperature, f() function of the decomposition degree, depending on the control mechanisms of the reaction, E energy of activation, R gas constant, T temperature, the energy of activation can be determined [5]:

E=
T, C

R[ln( d /d)2 - ln( d /d)]1 (1/T1) - (1/T2)

Fig. 1. TG curves of PVC in inert atmosphere.

100 80 =, % 60 40 20 0 0 200 T, C 400 600 4 C/min 10 C/min

Fig. 2. Degradation polytherms of PVC.

Fig. 3. Gas chromatography analysis of the thermally treated PVC.

252

J. Blazevska-Gilev, D. Spaseska

Fig. 4. Mass spectrometry analysis of the thermally treated PVC.

-12

25,33/exp(-1070330/RT) . 10-13

10

a)

40 35 30 25 20 15 10 5 0 0 0,5 1

b)

9,4/exp(-107033/RT)

0 0 0,2 0,4 " (1-= ) 0,6 0,8 1

" (1-= )

1,5

Fig. 5. Dependence of (d/d) / exp(-E/RT) on f() for the first region, with the heating rate of 4 o/min (a) and 10 /min (b).
o

In our case the value of the activation energy for the temperature region up to around 573 K is 107,033 kJ/mol, but for the region starting from 643 up to 723 K, the value is 212,840 kJ/mol which is in good correlation with the results of the authors Troitskii et al. [6] and Zaikov et al. [7]. The values d/d have been determined by using the relationship: d/d=( d/dT) ( dT/d). The value K0 is determined as tg(a) from the liner plots of (d/d) / exp(-E/RT) versus f() which passes through the origin of coordinates: Fig. 5 (a,b) and Fig. 6 (a,b). Concerning the first temperature region, the values on the ordinate is calculated by the relationship: 9,4/exp(-107033/RT).10-12 for the heating

rate of 4o/min, but for the heating rate of 10o/min, the valid relationship is as following: 25,33/exp(-1070330/ RT).10-13. For the second temperature region, the values on the ordinate are calculated by the two relationships, concerning the two different heating rates, 4 and 10oC/min: 1,319/exp(-212840/RT).10-19 and 3,298/exp(212840/RT).10-19, respectively. For the first region, by the heating rate of 4o/ min, there are two values for the magnitude K0: 3,125.1012 as a result of the validity of the model relationships for f(): (1)4. For the heating rate of 10o/min, the value of K0 is: 3,11.1013 depending on the model relationship validity: (1 )4. In the temperature region starting from

253

Journal of the University of Chemical Technology and Metallurgy, 45, 3, 2010

Table1. The values of K0 and the equations of Kf( ) for two thermal regions.
Temperature interval up to 573 K = 4 C min
o . -1

K0 (1-)
4

K f()

3,12.1012 3,12. 1012 exp(-107033/RT) (1-) 4 3,11.1013 3,11. 1013 exp(-107033/RT) (1-) 4 9,11 10 1,48 10
. . 19 20

= 10 oC. min-1 643-723 K = 4 C min

o . o . -1 -1

(1-)4 (1-) (1-)

6 6

9,11 10 exp(-212840/RT) (1-) 1,48 10 exp(-212840/RT) (1-)

80 60 40 20 0

. 20

19

4 4

= 10 C min
-19

1,319/exp(-212840/RT) 10

20

10

0 0 0,0005 0,001 0,0015

6

3,298/exp(-212840/RT) . 10-19

30

a)

b)

0,002

0,0025

0,001

0,002

0,003

Fig. 6. Dependence of (d/d) / exp(-E/RT) on f() for the second region, with the heating rate of 4 o/min (a) and 10 o/min (b) 643 up to 723 K, the values of K0 depending on the heating rates of 4 and 10o/min are: 9,11.1019 and 1,48.1020. The analytical shape of the kinetic curve f() is: (1 )6. Depending on the mechanism of the degradation process the analytical shape of the kinetic curve f() for the temperature interval up to around 573 K is presented with the model equation f()=(1)4, but for the temperature region from 643 up to around 723 K, is given by the model equation: f() =(1)6 (Table 1). The both model equations reveal the kinetic controlled mechanisms of the exampled process on macro level. The values of the pre-exponential factor K0, dependent on the slope of the degradation curves, are expressed different for the two examined steps of degradation. CONCLUSIONS The thermal degradation of PVC was analyzed in this paper on the basis of the released gas products as well as on the basis of a phenomenological model that describes the kinetics of the two separate temperature stages of the process. By means of the thermogravimetry and Gropjanov-Abbakumovs non-isothermal method for the investigation of the formal kinetic of PVC thermal degradation, the classical kinetics parameters like energy of activation and preexponential factor for the characteristic temperature regions have been determined. The analytical models of the kinetic curves for the two characteristic regions have been given. The adequacy of distinct equations in different temperature regions has been determined. REFERENCES 1. S.Chattopadhyay, G. Madras, Polymer Degradation and Stability, 78, 2002, 519-524. 2. E. Ranzi, M. Dente, T. Faravelli, G.Bozzano, S.Fabini, R. Nava, V. Cozzani, L. Tognotti, J. Anal. Appl. Pyrol., 40-41, 1999, 305-319. 3. T. Faravelli, G. Bozzano, C. Scassa, M. Perego, S. Fabini, E. Ranzi, M. Dente, J. Anal. Appl. Pyrol., 52, 1999, 87-103. 4. S. Moulay, Progress in Polymer Science, 35, Issue 3, 2010, 303-331. 5. V.M. Gropjanov, V.G. Abbakumov, Him. i him. tehnol. 18, 2, 1975, 202. 6. B.B.Troitskii, L.S.Troitskaya, Int. J. Polym. Mater., 41, 1998, 285. 7. G.E. Zaikov, K.Z. Gumargalieva, T.V. Pokholok, Y.V. Moiseev, V.G.Zaikov, Polym. Plast. Technol. Eng., 39, 2000, 567.

(1- )

(1- )

254