The Capacity of Lactams for Polymerisation as a Function of Their Structure

The capacity of lactams of different structures for polymerisation is considered from thermodynamic and kinetic standpoints. It is shown that the significant differences between the enthalpies of polymerisation can be accounted for by the presence of intramolecular hydrogen bonds and also by the resonance stabilisation of the cyclic amide. The probability of the polymerisation of lactams is determined kinetically by the chemical structure of the monomer, namely the conformation of the molecules (the presence of cis- and trans-isomers), the stabilisation of the amide group by the inductive, mesomeric, and hyperconjugation effects, the polarity of the molecules (the presence of hydrogen bonds or the occurrence of dipole–dipole interactions), and the basicity of the monomer.
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