Ionic polymerization energetics

The rate retarding role of water in radiation induced ionic polymerizations was visualized as proton extraction by water from the growing carbonium ion and hydronium ion formation (101). The formation of solvated hydronium ions is greatly favored energetically. 

Supramolecular stabilization means stabilization of certain chemical species, their different forms, and assemblies in a particular supramolecular environment. Supramolecular stabilization is responsible for the existence of "energetically unfavorable" conformations, different spatial isomers, unexpected oligomers, "unstable" molecules. highly reactive radicals, elements in unusual oxidation states, certain ionic species, and so on, in supramolecular phases. Such species decompose, change, or equilibrate with alternative forms once they are brought out of their "stabilizing" environment. The best-known chemical reaction based strictly on supramolecular stabilization is the so-called "blue reaction." where iodine reversibly polymerizes in the presence of starch. 

The fact that the rate of polymerization of crotonaldehyde increases with the dielectric constant of the solvent is evidence for an ionic mechanism of the polymerization. An increase in dielectric constant of the medium will favor energetically an increase in the rate of initiation and the stabilization of the zwitterion [172]. It should not influence the rate of propagation and termination. 

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