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Fast and Living Ring-Opening Polymerization of l-Lactide Initiated with In-situ–Generated Calcium Alkoxides

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Abstract

The ring-opening polymerization of l-lactide with calcium alkoxides generated in-situ from bis(tetrahydrofuran)calcium bis[bis(trimethylsilyl)amide] and 2-propanol are presented. The polymerization in THF at room temperature proceeds rapidly and in a living manner, giving poly(l-lactide)s of controlled molecular weight, low polydispersity, and tailored end-functionalities. Kinetic studies show the absence of an induction period and a pseudo-first order rate constant of 6.41 L mol−1 min−1, which is significantly higher than for related Y5(μ-O)(OiPr)13− or aluminum alkoxide-initiated polymerizations. The initiation involves a two-step process: (1) alcoholysis of bis(tetrahydrofuran)calcium bis[bis(trimethylsilyl)amide] to give the corresponding calcium alkoxide and (2) ring-opening of l-lactide via acyl-oxygen cleavage and insertion into the calcium-alkoxide bond. In the presence of excess alcohol, fast and reversible exchange between free alcohol molecules and coordinated alkoxide ligands takes place. This allows tuning of the poly(l-lactide) molecular weight over a wide range.

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Authors and Affiliations

  1. Department of Chemical Technology and Institute for Biomedical Technology, University of Twente, P.O. Box 217, 7500 AE, Enschede, The Netherlands

    Zhiyuan Zhong & Pieter J. Dijkstra

  2. Department Chemie der, Ludwig-Maximilians-Universität, Butenandstr. 9 (Haus D), D-81377, München, Germany

    Stefan Schneiderbauer & Matthias Westerhausen

Authors
  1. Zhiyuan Zhong
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  2. Stefan Schneiderbauer
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  3. Pieter J. Dijkstra
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  4. Matthias Westerhausen
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  5. Jan Feijen
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Zhong, Z., Schneiderbauer, S., Dijkstra, P.J. et al. Fast and Living Ring-Opening Polymerization of l-Lactide Initiated with In-situ–Generated Calcium Alkoxides. Journal of Polymers and the Environment 9, 31–38 (2001). https://doi.org/10.1023/A:1016092420618

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