Ring-opening polymerization of ε-caprolactone by lithium piperazinyl-aminephenolate complexes: synthesis, characterization and kinetic studies

Kerton, Francesca M. and Ikpo, Nduka and Hoffmann, Christian and Dawe, Louise N. (2012) Ring-opening polymerization of ε-caprolactone by lithium piperazinyl-aminephenolate complexes: synthesis, characterization and kinetic studies. Dalton Transactions, 41 (22). pp. 6651-6660. ISSN 1477-9234

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Abstract

A series of lithium complexes were prepared from 2(N-piperazinyl-N′-methyl)-2-methylene-4-R′-6-R-phenols ([ONN]RR′) and characterized through elemental analysis, 1H and 13C{1H} NMR spectroscopy, and X-ray crystallography. Treatment of the ligands with n-butyllithium afforded {Li[ONN]RR′}3 [R = Me, R′ = tBu, (1); R = R′ = tBu (2); R = R′ = tAm, (3), tAm = C(CH3)2CH2CH3], with trimetallic structures in the solid-state as shown by single-crystal X-ray diffraction. The reactivity of these complexes in the ring-opening polymerization of ε-caprolactone (ε-CL), as well as the influences of monomer concentration, monomer/Li molar ratio, polymerization temperature and time, was studied. Rates of polymerization were first order with respect to both monomer and lithium concentrations, and activation energies for the reactions were determined. MALDI-TOF MS analysis revealed that transesterification had occurred during the polymerization.

Item Type: Article
URI: http://research.library.mun.ca/id/eprint/5998
Item ID: 5998
Department(s): Science, Faculty of > Chemistry
Date: 30 March 2012
Date Type: Publication
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