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Kinetics, mechanisms and polymer property studies of ring-opening polymerization of ɛ-caprolactone and lactides initiated by (benzimidazolylmethyl)amino Zn(II) alkoxides

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Abstract

The reactions of substituted (benzimidazolylmethyl)amines ligands (L1–L3) with ZnEt2 in the presence of either BnOH or t-BuOH afforded the corresponding Zn(II) metal alkoxides [Zn(L1)(OBn)]2 (1), [(Zn(L2)(OBn)]2 (2), [Zn(L3)(OBn)]2 (3), [Zn(L2)(t-BuO)]2 (4), respectively. Complexes 1–4 formed effective initiators in the ring-opening polymerization (ROP) reactions of ɛ-caprolactone (ɛ-CL), D,L-lactide (D,L-LA) and L-lactide (L-LA). The ROP reactions followed pseudo-first-order kinetics with respect to monomer. Moderate molecular weight polymers of 10,650 g mol−1 exhibiting relatively narrow molecular weight distributions (1.16–1.54) were obtained. Predominantly crystalline isotactic poly(L-LA) and heterotactic poly(D,L-LA) were produced, respectively. Thermal analyses of PLA also supported the formation of isotactic poly(L-LA) with decomposition temperature of 298 °C.

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Acknowledgements

The authors would like to thank University of KwaZulu-Natal and National Research Foundation (NRF-South Africa) for financial support.

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Authors and Affiliations

  1. School of Chemistry and Physics, Westville Campus, University of KwaZulu-Natal, Private Bag X54001, Durban, 4000, South Africa

    Ekemini D. Akpan & Bernard Omondi

  2. School of Chemistry and Physics, Pietermaritzburg Campus, University of KwaZulu-Natal, Private Bag X01, Scottsville, 3209, South Africa

    Stephen O. Ojwach

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  1. Ekemini D. Akpan
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  2. Bernard Omondi
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Correspondence to Stephen O. Ojwach.

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289_2018_2321_MOESM1_ESM.docx

Supporting Information contains typical synthetic methods for the ligands and spectroscopic data, selected NMR and mass spectra of some complexes, kinetic plots and mass spectrum of polymers obtained. 1 (DOCX 664 kb)

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Akpan, E.D., Omondi, B. & Ojwach, S.O. Kinetics, mechanisms and polymer property studies of ring-opening polymerization of ɛ-caprolactone and lactides initiated by (benzimidazolylmethyl)amino Zn(II) alkoxides. Polym. Bull. 75, 5179–5195 (2018). https://doi.org/10.1007/s00289-018-2321-2

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  • DOI: https://doi.org/10.1007/s00289-018-2321-2

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