The kinetics of bulk polymerization of 6-, 7-, 9-, 12-, 13-, 16-, and 17-membered lactones initiated with a zinc 2-ethylhexanoate/butyl alcohol system at 100degreesC was studied and compared with that of lipase-catalyzed polymerization, Instantaneous concentrations of the lactone monomers were determined on the basis of the relative intensities of signals in the H-1 NMR spectra (500 MHz, CDCl3 as a solvent, room temperature) from the omega-methylene protons (-(CH2)(x-1)CH2OC(O)-) (where x = 4, 5, 7, 10, 11, 14, and 15) in the lactone monomer and the polyester repeating units, respectively. Linearity of the semilogarithmic kinetic dependencies (ln([lactone](o)/[actone]) vs time), revealed a first order of propagation in monomer for all of the polymerizations studied. This kinetic behavior, pointing to the constant concentration of the involved active centers and thus to the practical elimination of termination side reaction, allowed the relative polymerization rates to be determined. The following order of polymerization rates has been obtained: 2500:330:21:0.9:1.0:0.9:1.0 for the 6-, 7-, 9-, 12-, 13-, 16-, and 17-membered lactones, respectively. The order of rates of the enzymatic polymerization, determined earlier in an independent paper, shows an inverted dependence on the ring size, namely 0.10:0.13:0.19:0.74:1.0 for the 7-, 12-, 13-, 16-, and 17-membered lactones, respectively. The resulting difference in the orders of lactone reactivities in chemical and enzymatic polymerizations is explained in terms of a difference in factors controlling polymerization rates in both processes. The ring strain, which decreases with increasing lactone size, is partially released in the transition state of the elementary reaction of the polyester chain growth, which eventually leads to faster propagation for more strained monomers in chemical polymerizations. In enzymatic polymerizations, the rate-determining step involves formation of the lactone-lipase complex. The latter reaction is promoted by the hydrophobicity of the lactone monomer, which is higher for the larger lactone rings.
