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Thermal properties of lignin-based polycaprolactones

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Abstract

Lignin-based polycaprolactone (PCL) graft copolymers with various graft ratios were prepared by ring-opening reaction in order to design new lignin derivatives. Molecular length of PCL side chain was varied in a wide range, i.e. caprolactone/hydroxyl group (CL/OH) ratio was varied from 3 to 100 mol mol−1. The effect of lignin on thermal properties of PCL was examined by differential scanning calorimetry (DSC) and thermogravimetry. In DSC heating curves of lignin-based PCL, glass transition, pre-melt crystallization and melting were observed. From DSC results, the phase diagram of lignin-based PCL was established. It was found that glass transition temperature (Tg) decreased until CL/OH ratio reached 20, and then, Tg was maintained at around 200 K. Tg slightly increased when CL/OH ratio became higher than 20. The above facts suggest that the random structure of lignin affects the molecular motion of copolymers in a limited length of PCL chains, and that with increasing PCL chain length, free molecular motion is restricted by crystallization. The amorphous region of lignin–PCL was reorganized at pre-melt crystallization, and crystallinity increased. When CL/OH ratio increased more than 20, two melting peaks were observed; the low-temperature side is PCL crystallite affected by lignin and the high-temperature side melting peak is attributed to melting PCL crystal. The effect of lignin on thermal decomposition is apparently observed for lignin-based PCL when CL/OH ratio is smaller than 20. The above results suggest that lignin-based PCL graft copolymers have the potential of an applicant of novel nature-friendly polymers.

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Acknowledgements

We wish to express our thanks to Professor Clive S. Langham for his help with the preparation of the manuscript for this article.

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Authors and Affiliations

  1. Lignocel Research Co. Ltd., Ofunato, Tsukuba, 300-1267, Japan

    Tatsuko Hatakeyama & Hyoe Hatakeyama

  2. Fukui University of Technology, 3-6-1, Gakuen, Fukui, 910-8505, Japan

    Suzuka Yamashita & Hyoe Hatakeyama

Authors
  1. Tatsuko Hatakeyama
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  2. Suzuka Yamashita
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  3. Hyoe Hatakeyama
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Correspondence to Tatsuko Hatakeyama.

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Hatakeyama, T., Yamashita, S. & Hatakeyama, H. Thermal properties of lignin-based polycaprolactones. J Therm Anal Calorim 143, 203–211 (2021). https://doi.org/10.1007/s10973-019-09161-0

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