Thermodynamics and Kinetics of Ring - Opening Polymerization

Cyclic monomers that have been polymerized via ring opening encompass a variety of structures, such as alkanes, alkenes, compounds containing heteroatoms in the ring: oxygen [ethers, acetals, esters (lactones, lactides, and carbonates), and anhydrides], sulfur (polysulfur, sulfi des and polysulfi des), nitrogen [amines, amides (lactames), imides, N carboxyanhydrides and 1,3 oxaza derivatives], phosphorus (phosphates, phosphonates, phosphites, phosphines and phosphazenes), or silicon (siloxanes, silaethers, carbosilanes and silanes). For the majority of these monomers, convenient polymerization conditions have been elaborated, that result in the controlled synthesis of the corresponding polymers [1 – 13] . The ability of a cyclic monomer to polymerize according to the ring opening mechanism is determined by two equally important factors – the conversion of monomer molecules into macromolecules (of linear or more complex topologies) must be allowed both thermodynamically and kinetically. In practical terms this means that: (i) monomer macromolecule equilibrium must be shifted to the right hand (macromolecule) side; and (ii) the corresponding polymerization mechanism should exist, that could enable conversion of the monomer molecules into the polymer repeating units, within the operable polymerization time (Equation 1.1 ). The net equation of the polymerization process reads: