An Energetic Consideration of the Monomer Reactivity in Catalytic Polymerization

Publisher Website
Google Scholar
Abstract
The elementary processes constituting the polymerization reaction are energetically considered, and the relation between the activation energy of each process and the structures of reagents or the kind of solvents is theoretically discussed. The solvation energy of ion has been evaluated with the ionization potential of anion or the electron affinity of cation, and the ionization potential or the electron affinity of the growing radical with that of the corresponding monomer. The energy of the highest occupied (εho=α+λhoβ) or the lowest vacant (εlv=α–ηlvβ) π level of the monomer has been calculated, and the π bond dissociation energy has been evaluated with the summation (λho+ηlv). On the basis of these considerations, the monomer reactivity in catalytic polymerization can be compared with the relative magnitude of the electronic natures of monomer and components of catalyst, i. e., ionization potential or electron affinity.