L-lactide macromonomer synthesis initiated by new cyclic tin alkoxides functionalized for brushlike structures

L-Lactide macromonomers with an incorporated double bond were successfully synthesized by controlled ring-opening polymerization initiated by two new cyclic tin alkoxides (1,1-di-n-butyl-stanna-2,7-dioxacyclo-4-heptene and 9,9,20,20-tetrabutyl-8,10,19,21-tetraoxa-9,20-distanna-dispiro[5.5.5.5]docosa-2,14-diene). Initiators and crude reaction mixtures were characterized by NMR. H-1 NMR analysis showed that the initiators were completely reacted in the polymerization and that both tin-oxygen bonds were reactive and participated in propagation. The polymerizations were performed in chloroform at 60 degreesC, and the molecular weight was effectively controlled by adjusting the monomer-to-initiator ratio. The molecular weight distribution was narrow (<1.1) for both high and low molecular weights (3000-72 000 g/mol). A plot of M-n vs conversion was linear up to a conversion of 98%, showing a system propagating in a controlled manner. The kinetic investigation showed that all of the polymerizations were first order in monomer and that no termination reactions occurred during polymerization.