Polymer Degradation and Stability 39 (1993) 299-303

Kinetics of polymer degradation involving the
splitting off of small molecules: Part 9
thermal dehydrobromination of polyvinyl
Peter Simon
Department of Physical Chemistry, Faculty of Chemical Technology, Slovak Technical University, Radlinsk~ho 9,
812 37 Bratislava, Czechoslovakia

(Received 13 February 1992; accepted 1 March 1992)

High conversion kinetic runs of the thermal dehydrobromination of polyvinyl
bromide have been treated using the theory developed previously. The results
suggest that the dehydrobromination occurs most probably via the mechanism
of gradual zip growth where the initiation step of the zip reaction is not
autocatalytic. Good agreement between experimental and theoretical kinetic
curves has been achieved for this mechanism. The activation energy and
pre-exponential factor for random elimination of HBr are Ea = 153 kJ mo1-1
and log(A/s -1) = 13-7. The ratio of the rate constants of zip propagation and
random elimination decreases with increasing temperature.

INTRODUCTION corresponds to quantitative dehydrobrom-
ination. 6 During dehydrobromination, long pol-
Although polyvinyl bromide (PVBr) was one of yene sequences are formed which are longer than
the first vinyl polymers to be discovered, 1 it has in PVC dehydrochlorination. 9-11 This indicates
not been the subject of much study. Attention that the dehydrobromination occurs v i a the zip
has turned toward PVBr and vinyl bromide reaction. ~1The high-conversion kinetic curves are
copolymers only in the last two decades because S-shaped 12 which is typical of autocatalytic
of their flame-retardant properties. 2-8 Several reactions.
papers have been devoted to the degradation of In Part 3 of this series, the kinetic curves for
vinyl chloride/vinyl bromide copolymers for a the thermal dehydrochlorination of PVC in an
better understanding of the degradation of inert atmosphere were considered. 15 In Parts 4
PVC 9-n but we can only find one paper dealing and 5, autocatalytic mechanisms of polymer
with the thermal degradation of PVBr up to degradation which occur via elimination of
high conversions over a wide range of tempera- low-molecular weight compounds have been
tures. 12 analyzed 16,17 and the theory has been applied to
PVBr is substantially less stable than PVC but the study of the thermal degradation of PVC in
in most respects it shows analogous degradation HCI and oxidative atmospheres 18"19 and to the
behaviour. 6 Decomposition of PVBr begins at degradation of polyvinyl esters TM (Parts 6-8). The
about 100°C 12,13 and up to 270°C, de- aim of this present paper is to use the theory for
hydrobromination is the dominating reaction. 14 the treatment of experimental data on the
Ostromysslenskii was the first to report that large thermal dehydrobromination of PVBr in an inert
quantities of HBr are liberated when PVBr is atmosphere published by Mazon-Arechederra et
heated to 220°C. 1 The weight loss of PVBr al. 12


The agreement between theory and kinetic equation where the main feature of the experiment is very good.7 153 10-4 96 0-014 4 0-999 0. E~. For the simulation of kinetic curves the same Two minima have been found for the model of procedure is used as in Parts 3. Ea. the kinetic equations minimum is not so deep as the other. AE~. It follows of gradual zip growth. that the theory adequately describes the ex- For the model of immediate zip growth. For example. Po and xm. thus pointing to the fact involved. 15'18'19 This should be the case since the minimized parameters are A. is not exhibit any regularity.300 Peter ~imon S I M U L A T I O N OF T H E KINETIC C U R V E S Part 8 and the minimized parameters are A. o 13.024 1 15-9 206 4-9 14 6 × 10 . AEy. the values of the parameters seem to be for the minimization of the sum of squares more reasonable for the first minimum where the between experimental and calculated values of activation energy of random dehydrobromina- conversion are A. the zip reaction. which is approxim- ately equal to the conjugation energy of two double bonds. 6 The difference between the individual parameters are given in Part 6.e. AEa. both eqn (7) in Part 4 as well as eqn (13) of conversion for the first minimum are shown in in Part 5 degenerate into a simple autocatalytic Fig. at is not autocatalytic. The deviations combination of Ay and E~ leading to 7--->0. C--CI bond energy is higher than the energy of AA#. the kinetics are activation energy for PVC dehydrochlor- described by eqns (13) and (14) in Part 5 and the ination. the pre-exponential factor for de- hardly possible to be immediate. AAr. In the case of Table 1. Kinetic parameters for the degradation of PVBr Iog(A/s-1) Ea/kJ mol ' Iog(A~/s-~) EJkJ tool-1 po x. is . The meanings of the C . The values of parameters temperatures is treated simultaneously. between the calculated and experimental values Then. the growths 16'17 has been examined here.. the ratio of rate constants of random Part 5 are thus reduced to eqns (1) and (2) in elimination for PVBr and PVC is about 800. The deviations do not degradation of PVBr. which random elimination. AA.B r bond. by leading to very low values of B and to values of 17kJmo1-1. For the model hydrobromination of PVBr is higher.5 7 kJ mo1-1. For gradual zip growth. 7 and 8.e.. is higher for PVBr than means that the initiation step of the zip reaction for PVC at any temperature. are summarized in tested to fit the experimental data. the perimental data. ~5 More- 10-5-10 -4 . 1. minimum corresponding to the zip reaction has The activation energy of random de- been found for the combination of parameters hydrobromination of PVBr is less. 22 For these reasons.. Ea. Equations (13) and (14) in 190°C. Po and x. AA~. The growth of such long zips seems over. AEa. than the corresponding activation m of the order 105 where the value of Po is about energy for PVC dehydrochlorination. AEr. or. AA m AE m Po tion. gradual zip growth without the autocatalytic the whole set of kinetic runs measured at various initiation step. Models corresponding to the minima and the standard of both immediate and gradual zip growth 16'17 are deviations per mesh point. the parameters AAa and from eqn (1) in Part 3 that the rate constant of AEa have always led to the value fl---)0. B.7 0-959 0-016 4 . i. In both kinetic parameters corresponding to the first cases. i. Ea. activation energies of propagation and initiation steps. is lower than the corresponding and xm.. As the values of 0 show. 21 This decrease is in accordance RESULTS AND DISCUSSION with the idea that the origin of the allylic activation consists in the conjugation of the The possibility of the occurrence of the transition state of dehydrohalogenation with the mechanisms of immediate and gradual zip adjoining C----C bond. for the minimum is a little deeper. Despite are eqns (7) and (8) in Part 4 and the parameters this. 6. a minimum has been found for the minimum in Table 1 appear to be more combination of the parameters AA and AEa reasonable and acceptable even though the other leading to the value m ~ l or.. Table 1.. the first the immediate zip growth.

occurrence of structural defects greatly affects the x position of the maximum rate. In eqn (1) in Part 8. In Part 5 we have Ey = E.x X ×: O • ++ XAX x • • &&A D• X th 4-+ + N [] 0"04 - -t- + 0"0B . propagation and random initiation.4 . As shown by Fig. an opposite trend is 8 encountered in the dehydrobromination of PVBr. 2. the greater is ~. ¢. + AEr (2) examined how the conversion at which the maximum rate is reached. ~. Temperatures: (1) 150°C. 7 of A~ and Er can be calculated as decreases with increasing temperature. Arrows indicate the conversion at which cide perfectly with the calculated values. Comparison of eqns (9) and (10) in Part 5 . according to eqn (2) in Part 6.zJz). [] I I I I Fig. 7 has values 1 200-11 000. the fraction of growing zips exhibits a maximum. where zd/z is expressed by eqn (21) in Part 5. ~7 the values Consequently. This shows that not only the ! u value of 7.2 . (A) 160°C. Since 7 is the ratio of the rate constants of zip Table 1 shows that E~ is less than Ea. Deviations between the calculated and experimental values of conversion for the dehydrobromination of P V B r 12 Temperatures: (O) 130°C. (O) 140°C. zd. For f l = 0 and Po=O it has been found that the greater the value of 7. Dependences of the rate of dehydrobromination on conversion (calculated values). but also the probability of the 0 . o . The value of 7 decreases with increasing temperature. As illustrated in Fig. The positions of Fig. (A) 170°C. the position of which is almost identical with the position of the maximum rate. AA~ (1) tion.6 . the fraction of growing zips is given by the term ( 1 .8 !. (x) 150°C. (+) 145°C. 2. the maximum rate is reached. 3. but the conversion ¢ increases. For the temperature region of PVBr dehydrobromina- A ~ = A . (3) 170°C. Thermal dehydrobrominationof polyvinyl bromide 301 O'OB A A & AA Z~ 0"04 AA A A A x X u +4. depends on 7. (D) 190°C. 1. (2) the maximum rate found experimentally 12 coin- 160°C. This behaviour is obviously the consequence of structural defects in the polymer chain causing premature zip termination.

Thermochim. K.. & when the interconnection of zips is more intense... structural irregularities plays an important role. Then the number of HBr molecules produced by 19 (1975) 1079. & Thallmaier. Boylston. 99 (1966) 59. T. Nazarova.. Chem. : Part C. I. A. 4. J. Braun. 17 Our results thus indicate that at first sight. & but also when premature zip termination due to Neumeyer. 240. and the maximum of p.2 . 2.za/z)yp (3) or is delayed.. Sci. M. 3... & Gibov.. Chem. R. P. 414 dehydrobromination. Iv~in. I. B. Kelen. J. 4 demonstrates. 21 (1983) 3249. p are higher for lower temperatures. the model of gradual zip growth whereas G.. 7. Obviously. D. 9. Braun. This conclusion is in real chain the dependences of p on x also exhibit agreement with Braun et ai. p increases with the probability p. J. models resides in the consideration of zip 11. The ratio p attains its (1912) 204. Chem. Makromol. Fig. B.. Braun. the values of Sci. 16 growth. X X Fig.. in the model of gradual zip growth it is assumed that zip termination does not take place p = (1 . S.. H. Diab. dehydrochlorination of PVC in an inert atmos. at the conversion corresponding to the maximum dehydrobromination rate. Vysokomol. M... Ed.. J. I. Sci. A. zip termination is considered. Hobart. B6hringer. J. Fraction of growing zips as a function of conversion. considerable differences and termination is higher for vinyl chloride/vinyl exist between the positions of the maximum rate bromide copolymers than for PVC. Ed. 2. Ratio of the rates of zip propagation and random Temperatures and arrows as in Fig.6 • 1. Polym. In the model of immediate zip dehydrobromination due to zip propagation and growth. M6ri.4 40 . P. for a the rate of zip termination.. Diab. Dehydrobromination of PVBr is described by 8. BI$ (1976) 50. : Polym. 16 (1976) 149. A. Polym. maximum at much higher conversions not only 2. C.11 who have observed maxima. J. On the the rate of random elimination of HBr is given by contrary. 37 (1986) 390.3 30 20 10 0 . Straiton. Donaldson. elimination as a function of conversion.. Acta Polymerica. : Polym. A. 0 . T. Temperatures and arrows as in Fig. Appl. M. Karzhaubaeva. L. . Chem. 18 (1980) 2085.302 Peter ~imon P ! . 16 (1976) 133. Wadsworth.. Mack... Due to higher values of y. 3. Phys. 5. K... leads to the result that the ratio of the rate of termination. phere obeys the model of immediate zip 10. E. propagation per random elimination decreases 6. P. rapidly. 15 The main difference between the two (1967) 2351. Thermochim. As Fig. C. B.. J. Soc. Russ. Mack. the position of which depends on that the ratio of rate constants of zip propagation temperature.4 . D.2 . Sci. L. R. the rate of zip propagation in PVBr deo This is undoubtedly the case for an ideal polymer hydrobromination is incomparably higher than chain when zd = 0. However. Acta.. McNeill. N. interconnection of zips REFERENCES predominates over the formation of new zips thus leading to the decrease in the rate of 1.. J. & Anderson. E. S.. Zhubanov. 4. D. Acta.4 . Polym. C. Knoepfler. Ostromysslenskii.. J. Polym. B. Soedin. H. M. D.. & Muller. 1. & Thallmaier. Neumeyer. M..

. Poly. Delgado Quintero. Deg.0 (1982) 25. Simon. Montaudo. Scamporrino.. Deg. 14. and Stab. Deg. & Vitalini. 2. 38 Chem. C. Simon. Low. J. 12. Poly.. M. M. Poly.. . M. and Stab. 21. M.. D.. Ed. E. & Monterra.. 13. Simon. P. 35 (1992) 45.. 35 (1992) Barrales-Rienda. P. P. Simon... Mater. 20. Polym. Polym.. Simon. : Polym. 143 (1986) 16. Deg. and Stab. Deg. Polym. Phys. O'Shea. : Polym. & 18. Puglisi. & Valko. Makromol. L. & Ryb~r... P. 19. Chem. and Stab. & Valko. A. 165. 29 (1990) 263.. Poly. C... 249.. Chem.. P. Angew. Simon. Simon. 22. 2.. J.. Sci. M. and Stab.. D.. Ed. P... J. J. 36 (1992) 85. Maz6n-Arechederra. Poly. & Valko.3 (1989) 499. P. P. & Simon. 99 (1985) 447. J.. 15. Poly.. (1992) 255. Valko. 24 (1986) 301. Gatial. and 25 (1989) 245. Chem.. J.. Thermal dehydrobromination of polyvinyl bromide 303 & Tiid6s. L. 17. Phys. 35 (1992) 157. M.. L.. G. P. Europ. Sci. Deg. P. L. F. Stab. L. Chem. (~ernay.