Ionic and Coordination Ring‐Opening Polymerization

Abstract This article provides the up‐to‐date and comprehensive review (over 700 citations) of all the important subjects of the ring‐opening polymerization (ROP) methods of polymers syntheses. This is the method of synthesis of several important classes of polymers that cannot be prepared in a different way (e.g., polyethers). It also complements known methods of polycondensation and ROP often is the method of choice. ROP is particularly important in syntheses of the biodegradable polymers‐polylactide and poly(ε‐caprolactone), discussed in details. Applications of these polymers, as well as polysiloxanes in biomedical applications are irreplaceable in the modern medicine. Either as bulk polymers or as nano‐ and microspheres, described In this article separately. There are sections in the present version that were not presented in the previous editions. This is description of polyoxazolines, polymers with phosphorus atoms in the chains, as well as mentioned above polysiloxanes an microspheres. We introduced also section describing novel analytical methods, particularly useful in studies of polymers with various architectures (star shape, multibranched etc.). Besides the synthetic aspects of ROP, this article describes thermodynamics and kinetic features of the living/controlled polymerizations, particularly by activated monomer mechanism and importance of dormant polymers in precision syntheses of desired structures.