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Polymer Bulletin

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14-06-2017 | Original Paper

Use of samarium(III)–amino acid complexes as initiators of ring-opening polymerization of cyclic esters

Authors: Dimas A. Medina, Jesús M. Contreras, Francisco J. López-Carrasquero, Eduardo J. Cardozo, Ricardo R. Contreras

Published in: Polymer Bulletin | Issue 3/2018

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Abstract

Poly(ε-caprolactone) (PCL) and poly(l-lactide) (PLA) were prepared by ring-opening polymerization (ROP) using samarium(III) acetate (SmAc₃) and amino acid complexes of samarium(III) as initiators. The catalytic behavior of samarium(III) acetate and their respective amino acid complexes, Sm(2,2′-bipyridine)(Lⁿ)₃ (L¹ = l-aspartic acid; L² = l-glutamic acid and L³ = glycine), was studied. It could be observed that the amino acid structure and chemical bond type have great influence on the catalytic activity. Polymerization reaction temperature was 125 °C and the effect of time reaction on the conversion of monomers to polymers and the molecular weight were studied. The results indicate that the initiators induce the polymerization of ε-caprolactone (ε-CL) and l-lactide (l-LA). Polymers were characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance (¹H-NMR) and size exclusion chromatography (SEC). Polyesters with average-number molar mass of 1.50 × 10³ − 10⁴ Da were obtained. Based on the ¹H-NMR end group analysis of low molecular weight of polymers, a coordination–insertion mechanism is proposed for the polymerization of lactones. Kinetics study indicated a polymerization rate of first order with respect to monomer concentration. Differences in the rates of polymerization in the four initiators appeared to be governed by the different degrees of steric hindrance in the initiator structure and monomer.

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Title: Use of samarium(III)–amino acid complexes as initiators of ring-opening polymerization of cyclic esters
Authors: Dimas A. Medina
Jesús M. Contreras
Francisco J. López-Carrasquero
Eduardo J. Cardozo
Ricardo R. Contreras
Publication date: 14-06-2017
Publisher: Springer Berlin Heidelberg
Published in: Polymer Bulletin / Issue 3/2018
Print ISSN: 0170-0839
Electronic ISSN: 1436-2449
DOI: https://doi.org/10.1007/s00289-017-2089-9

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