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ε-caprolactone ring-opening polymerization catalyzed by imidazolium-based ionic liquid under mild reaction conditions

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Abstract

Polycaprolactone is a biodegradable, biocompatible, and versatile polymer commonly used in the pharmaceutical and biomedical industry and the development of new catalysts that allow for the synthesis under milder reaction conditions and in shorter reaction times is an appealing alternative. The iron-containing imidazolium-based ionic liquid 1-n-butyl-3-methylimidazolium heptachlorodiferrate was able to efficiently catalyze the ring-opening polymerization of ε-caprolactone under mild reaction conditions. Polymerization yields higher than 80% were obtained after 4 h of reaction at temperatures up to 85 °C, using low ionic liquid:ε-caprolactone molar ratios (1:720 − 1:1500), in the absence of solvent and without an intentionally added alcohol as an initiator. Semi-crystalline polycaprolactones, with molecular weights up to 14 kDa and narrow molecular weight distributions were synthesized. The chemical structure of the polymer was confirmed by Nuclear Magnetic Resonance (1H NMR) and Fourier Transform Infrared (FTIR) spectroscopy, and its crystalline content was estimated from the enthalpy of melting of the differential scanning calorimetry (DSC) thermogram. Finally, a caprolactone-activated ROP mechanism mediated by the ionic liquid was suggested.

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Availability of data and material

The datasets generated during the current study are available from the corresponding author on request.

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Acknowledgements

The authors thank the financial support from CAPES − Coordenação de Aperfeiçoamento de Pessoal de Nível Superior, Finance Code 001 and CAPES PRINT Program (Project Number: 88887.310560/2018-00), and CNPq − Conselho Nacional de Desenvolvimento Científico e Tecnológico. The authors also thank the Analysis Center of Chemical Engineering and Food Engineering Department from the Federal University of Santa Catarina for the DSC analysis.

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Authors and Affiliations

  1. Department of Chemical Engineering and Food Engineering, Federal University of Santa Catarina, Campus Reitor João David Ferreira Lima, Florianópolis, SC, 88040-900, Brazil

    Monique J. Leite, Tamara Agner, Pedro H. H. Araujo & Claudia Sayer

  2. Chemistry Institute, University of Brasília, Campus Universitário Darcy Ribeiro, Brasília, DF, 70910-900, Brazil

    Fabricio Machado & Brenno A. D. Neto

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  1. Monique J. Leite
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Correspondence to Claudia Sayer.

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Leite, M.J., Agner, T., Machado, F. et al. ε-caprolactone ring-opening polymerization catalyzed by imidazolium-based ionic liquid under mild reaction conditions. J Polym Res 29, 56 (2022). https://doi.org/10.1007/s10965-022-02891-0

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