Abstract
Kinetics of the polymerization of L-lactide (LA) and e-caprolactone (CL) initiated with dialkylaluminum alkoxide, aluminum trialkoxide and related metal alkoxides is reviewed. The former give aggregating active species, and a method is described allowing simultaneous determination of the rate constants of propagation and aggregation equilibrium constants. It has been shown that tin“ dicarboxylate (dioctoate) requires a coinitiator in order to start polymerization. Both kinetic and spectroscopic evidence indicate that propagation proceeds on the —Sn-OR bonds. The major reaction accompanying propagation is the chain transfer-to polymer; either inter or intramolecular. Methods are described giving access to the rate constants of both transfers Finally, correlation is given between the atomic number of metal involved in the active species and the determined rate constants: the larger the atomic number, the higher is the rate constant of propagation and the less selective is the polymerization process.
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