Activation Energies of the Decomposition of Poly(methyl α-phenylacrylate) from Static and Dynamic TGA

  • G. G. Cameron
  • G. P. Kerr


It is shown that good agreement between activation energies, Ea, as determined by the two methods occurs only when the mechanism of degradation is invariant with extent of decomposition. In the case of poly(methyl α-phenylacrylate), which decomposes by random initiation and unzipping to monomer, this condition only applies with low-molecular-weight material. In polymers which contain long chains a termination step reduces Ea. As the amount of termination diminishes with average molecular weight (i.e., with extent of reaction) Ea from dynamic TGA is an average. Ea from static TGA (initial conditions) does not suffer from this disadvantage.


Methyl Methacrylate Termination Step Polymer Decomposition Kinetic Chain Length Dynamic Thermogravimetric Analysis 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    J. H. Flynn and L. A. Wall, General treatment of the thermo- gravimetry of polymers, J. Res. Nat. Bur. Standards U. S., 70A, 487 (1966).Google Scholar
  2. 2.
    H. Hopff, H. Lüssi, and L. Borla, Zur Polymerisation des Atropasäuremethylesters, Makromolek, Chem., 81, 268 (1965).Google Scholar
  3. 3.
    G. G. Cameron and G. P. Kerr, unpublished results.Google Scholar
  4. 4.
    K. Chikanishi and T. Tsuruta, Reactivity of a-alkylacrylic esters. Part 1. Homopolymerisation behaviors of methyl oalkylacrylates, Makromolek. Chem., 81, 198 (1965).Google Scholar
  5. 5.
    H. H. G. Jellinek and M. D. Luh, Thermal degradation of isotactic and syndiotactic poly(methyl methacrylate), J. Phys. Chem., 70, 3672 (1966)Google Scholar
  6. 6.
    D. W. Brown and L. A. Wall, Pyrolysis of poly(a-methylstyrene), J. Phys. Chem„ 62, 848 (1958).CrossRefGoogle Scholar
  7. 7.
    E.S. Freeman and B. Carroll, The application of thermoanalytical techniques to reaction kinetics, J. Phys. Chem., 62, 394 (1958).CrossRefGoogle Scholar
  8. 8.
    D. A. Anderson and E. S. Freeman, The kinetics of the thermal degradation of polystyrene and polyethylene, J. Polymer Sci., 54, 253 (1961).CrossRefGoogle Scholar
  9. 9.
    L. A. Wall and J. H. Flynn, Degradation of polymers, Rubber Chem. and Technol„ 35, 1157 (1962).CrossRefGoogle Scholar
  10. 10.
    L. A. Wall, Polymer decomposition: thermodynamics, mechanisms, and energetics, SPE J., 16, 810 (1960).Google Scholar
  11. 11.
    G. G. Cameron and G. P. Kerr, Simultaneous occurrence of chain-end and random initiation during thermal degradation of poly(methyl methacrylate), Makromolek. Chem., 115, 268 (1968).Google Scholar

Copyright information

© Plenum Press, New York 1970

Authors and Affiliations

  • G. G. Cameron
    • 1
  • G. P. Kerr
    • 1
  1. 1.Department of ChemistryUniversity of AberdeenOld AberdeenScotland

Personalised recommendations