Selective Transesterification to Control Copolymer Microstructure in the Ring-Opening Copolymerization of Lactide and ε-Caprolactone by Lanthanum Complexes.

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A series of novel lanthanum amido complexes, supported by ligands designed around the salan framework (salan = N,N'-bis(o-hydroxy, m-di-tert-butylbenzyl)-1,2-diaminoethane) were synthesized and fully characterized in the solid and solution states. The ligands incorporate benzyl or 2-pyridyl substituents at each tertiary amine center. The complexes were investigated as catalysts in the ring-opening homopolymerization of lactide (LA) and ε-caprolactone (ε-CL) and copolymerization of equimolar amounts of LA and ε-CL at ambient temperature. Solvent (THF or toluene) and the number of 2-pyridyl groups in the complex were found to influence the reactivity of the catalysts in copolymerization reactions. In all cases, complete conversion of LA to PLA was observed. The use of THF, a coordinating solvent, suppressed ε-CL polymerization, while the presence of one or more 2-pyridyl groups promoted ε-CL polymerization. Each copolymer gave a monomodal trace in gel permeation chromatography-size-exclusion chromatography (GPC-SEC) experiments, indicative of copolymer formation over homopolymerization. Copolymer microstructure was found to be dependent on catalyst structure and reaction solvent, ranging from blocky to close to alternating. Experiments revealed rapid conversion of LA in the initial stages of the reaction, followed by incorporation of ε-CL into the copolymer by either transesterification or propagation reactions. Significantly, the mode of transesterification (TI or TII) that occurs is determined by the structure of the metal complex and the reaction solvent, leading to the possibility of controlling copolymer microstructure through catalyst design.