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Kinetic and mechanistic investigation of the ring-opening polymerization of l-lactide initiated by nBu3SnOnBu using 1H-NMR

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Abstract

The kinetics of the ring-opening polymerization (ROP) of l-lactide (LL) initiated by tri-n-butyltin n-butoxide (nBu3SnOnBu) was investigated by proton nuclear magnetic resonance spectroscopy (1H-NMR). The kinetic parameters such as the rate constant (k) and the activation energy (E a ) were determined. The values of k increased with increasing temperature and initiator concentration. The E a values determined from the ROP of LL initiated by 1.0, 1.5 and 2.0 mol% of nBu3SnOnBu were 95.9, 87.8 and 72.4 kJ/mol. The molecular weight of poly(l-lactide) (PLL) was successfully controlled by adjusting nBu3SnOnBu concentration. Furthermore, the number average molecular weight (\(\bar{M}_{n}\)) of these polymers was in the range of 1.1 × 104–3.2 × 104 with molecular weight distribution of 1.4–1.9 and the molecular weight of PLL was higher than poly(ε-caprolactone) under identical synthesis conditions. Furthermore, the molecular weight of the synthesized polymers was lower than the theoretical values (\(\bar{M}_{n}\)(cal)) indicating the occurrence of transesterification.

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Acknowledgments

W. Limwanich would like to thank the Research Professional Development Project under the Science Achievement Scholarship of Thailand (SAST) for graduate fellowship. The authors wish to thank the financial supports from the National Research Council of Thailand (NRCT) and the National Research University Project under Thailand’s Office of the Higher Education Commission. Department of Chemistry, Faculty of Science and the Graduate School of Chiang Mai University are also acknowledged.

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Authors and Affiliations

  1. Polymer Research Laboratory, Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai, 50200, Thailand

    Wanich Limwanich, Puttinan Meepowpan, Nawee Kungwan & Winita Punyodom

  2. Faculty of Sciences and Agricultural Technology, Rajamangala University of Technology Lanna, Chiang Mai, 50300, Thailand

    Wanich Limwanich

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  1. Wanich Limwanich
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Correspondence to Winita Punyodom.

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Limwanich, W., Meepowpan, P., Kungwan, N. et al. Kinetic and mechanistic investigation of the ring-opening polymerization of l-lactide initiated by nBu3SnOnBu using 1H-NMR. Reac Kinet Mech Cat 119, 381–392 (2016). https://doi.org/10.1007/s11144-016-1062-1

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  • DOI: https://doi.org/10.1007/s11144-016-1062-1

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