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Microwave-assisted solvent-free ring-opening polymerization of ε-caprolactone initiated by n-butyltin(IV) chlorides

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Abstract

The microwave irradiation was successfully and firstly used to improve the solvent-free ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) with different n-butyltin(IV) chloride (nBumSnCln; m and n = 1–3) initiators such as tri-n-butyltin(IV) chloride (nBu3SnCl), di-n-butyltin(IV) dichloride (nBu2SnCl2), n-butyltin(IV) trichloride (nBuSnCl3). The performance of these n-butyltin(IV) chloride initiators in the synthesis of poly(ε-caprolactone) (PCL) was benchmarked and compared to the conventional initiating system of tin(II) 2-ethylhexanoate (Sn(Oct)2). The ROP of ε-CL with all initiating systems was completed in a short time of 30 min by using microwave power of 450 W. The chlorine (Cl) atom presented in the nBumSnCln initiators played an important role in the molecular weight of PCL. The higher amount of Cl in nBumSnCln and the lower PCL molecular weight were obtained. Under the condition used in this work, the performance of initiating systems in the synthesis of PCL via microwave irradiation was in the following order: nBu3SnCl > nBu2SnCl2 > nBuSnCl3 ≈ Sn(Oct)2. Surprisingly, the slowest nBu3SnCl initiator produced the highest weight average molecular weight (Mw = 6.31 × 104 g/mol) of PCL under microwave irradiation and solvent-free condition. The dispersity (Đ) of the synthesized PCL became narrower (Đ = 1.39–1.90) when the nBu3SnCl initiator was used instead of other initiating systems (Đ = 1.62–2.34). The synthesized PCLs were characterized by the Fourier transform infrared spectroscopy (FTIR), proton and carbon-nuclear magnetic resonance spectroscopy (1H- and 13C-NMR), and gel permeation chromatography (GPC) techniques. The mechanism of the ROP of ε-CL with all initiating systems was also explained. The microwave irradiation by a commercial microwave oven could be considered as an effective route in terms of the cost-effective and short synthesis time for biodegradable polymer production.

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Acknowledgements

This research project was supported by Fundamental Fund 2023 (grant number 2566FF062), Rajamangala University of Technology Lanna (W. Limwanich). We also would like to thank Center of Excellence in Materials Science and Technology, Chiang Mai University for partial support. Faculty of Science and Agricultural Technology, Rajamangala University of Technology Lanna was also acknowledged for the support of FTIR measurement. We would like to thank Department of Chemistry, Faculty of Science, Chiang Mai University for the support of NMR analysis.

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Authors and Affiliations

  1. Faculty of Science and Agricultural Technology, Rajamangala University of Technology Lanna, Chiang Mai, 50300, Thailand

    Watcharee Funfuenha & Wanich Limwanich

  2. Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai, 50200, Thailand

    Winita Punyodom & Puttinan Meepowpan

  3. Center of Excellence in Materials Science and Technology, Chiang Mai University, Chiang Mai, 50200, Thailand

    Winita Punyodom & Puttinan Meepowpan

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  1. Watcharee Funfuenha
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Correspondence to Wanich Limwanich.

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Funfuenha, W., Punyodom, W., Meepowpan, P. et al. Microwave-assisted solvent-free ring-opening polymerization of ε-caprolactone initiated by n-butyltin(IV) chlorides. Polym. Bull. 81, 475–490 (2024). https://doi.org/10.1007/s00289-023-04720-w

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