Immortal polymerization: The outset, development, and application

The story of the outset of the concept of immortal polymerization is presented. Immortal polymerization is the polymerization that gives polymers with a narrow molecular distribution, even in the presence of a chain transfer reaction, because of its reversibility, which leads to the revival of the polymers once dead, that is, the immortal nature of the polymers. As a result, immortal polymerization can afford polymers with a controlled molecular weight, the number of polymer molecules being more than that of the initiator. The compound that plays a leading role is metalloporphyrin, in which the metal-axial ligand bond has an unusually high reactivity. Immortal polymerization can be carried out in the ring-opening polymerizations of epoxides, episulfides, and lactones by the selection of an appropriate metalloporphyrin as the initiator and a protic compound as the chain transfer agent. Immortal polymerization is an effective method for synthesizing end-functional polymers and oligomers with narrow molecular weight distributions. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2861–2871, 2000