Thermodynamic and Kinetic Polymerizability

Thermodynamic and kinetic polymerizabilities are discussed in terms of the influence of monomer structure on the thermodynamic potentials ( G, F, H , and S ) and ceiling temperatures ( T c ) as well as on the rate constants of propagation and composition of the active centers. Up-to-date definitions for major thermodynamic parameters (based on the IUPAC documents) are presented and particularly clear distinction is given between the usual equilibrium monomer concentrations [M] e and particular ceiling monomer concentrations [M] c as determined for [M] o  = 1 mol l −1 and for bulk polymerization. For establishing thermodynamic polymerizability – a major factor deciding whether a given compound is able to form long chains – either Gibbs energy of polymerization or ceiling temperatures could be applied.