Macromolecules, Vol.29, No.19, 6132-6138, 1996
Kinetics and Mechanism of L-Lactide Polymerization Using 2 Different Yttrium Alkoxides as Initiators
Polymerization of L-lactide in dichloromethane at 25 degrees C using an initiating system comprising tris(2,6-di-tert-butylphenoxy)yttrium and 2-propanol was first order in monomer and initiator. A propagation rate constant of 1.92 x 10(3) L mol(-1) min(-1) was determined using in situ UV spectroscopy. In the first step the large 2,6-di-tert-butylphenoxy ligands are exchanged for the sterically less demanding 2-propoxide ligands. In the second step the alkoxide is able to attack the carbonyl group with formation of the ring-opened product. After the first two initiating steps the polymerization can proceed until the equilibrium conversion of monomer is reached. Evidence for these three steps is provided by H-1 and C-13 NMR spectroscopy of the reaction products of each step. The kinetic behavior of commercially available yttrium isopropoxide was more complicated.
Keywords:MOLECULAR-WEIGHT DISTRIBUTION;ANIONIC-POLYMERIZATION;EPSILON-CAPROLACTONE;CATIONIC POLYMERIZATION;LIVING POLYMERIZATION;CRYSTAL-STRUCTURE;ACTIVE-CENTERS;LACTONES;POLYLACTONES;SCANDIUM