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Kinetics of Sn(Oct)2-catalyzed ring opening polymerization of ε-caprolactone

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Abstract

To evaluate the effects of different alcohols (primary, secondary, and two different tertiary alcohols) as initiators on the structure of polycaprolactone (PCL) in ring-opening polymerization (ROP), four experiments were conducted in toluene with tin(II) 2-ethylhexanoate (Sn(Oct)2) as the catalyst. The kinetics of ε-caprolactone (ε-CL) ROP at different temperatures and monomer concentrations were studied with n-butanol as the initiator and Sn(Oct)2 as the catalyst. The kinetic plot of ln(M0/Mt) vs. time (t) seems a linear, which indicates that the propagation rate is in the first order with respect to monomer concentration. When the reaction temperature increased, the reaction rate and the final relative maximum monomer conversions also increased. The molecular weight of PCL initially increased and then decreased as monomer conversion increased. This behavior can be attributed to the high viscosity of the system, which affected monomer diffusion and polymer chain propagation. In addition, prolonging reaction time caused inter-/intramolecular transesterification. However, when monomer concentration decreased, the reaction rate decreased. The actual activation energy of Sn(Oct)2-catalyzed ROP of ε-CL in toluene was -75 kJ/mol.

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Acknowledgements

We gratefully acknowledge financial support from the National Natural Science Foundation of China (No. 21464012 and No. 21661027), Program for Changjiang Scholars and Innovative Research Team in University (No. IRT_15R46), Funds for Distinguished Young Scientists of Xinjiang Bintuan (No. 2014CD001) and Scientific Research Program of Shihezi University (No. RCZX201407).

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Authors and Affiliations

  1. Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan / School of Chemistry and Chemical Engineering, Shihezi University, Shihezi, P. R. China

    Dan Wu, Yin Lv, Rui Guo, Jiahui Li, Aerman Habadati, Bowen Lu, Heyun Wang & Zhong Wei

  2. Key Laboratory of Materials-Oriented Chemical Engineering of Xinjiang Uygur Autonomous Region / Engineering Research Center of Materials-Oriented Chemical Engineering of Xinjiang Bingtuan, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi, P. R. China

    Yin Lv

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  1. Dan Wu
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  2. Yin Lv
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  3. Rui Guo
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Correspondence to Zhong Wei.

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Wu, D., Lv, Y., Guo, R. et al. Kinetics of Sn(Oct)2-catalyzed ring opening polymerization of ε-caprolactone. Macromol. Res. 25, 1070–1075 (2017). https://doi.org/10.1007/s13233-017-5148-z

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  • DOI: https://doi.org/10.1007/s13233-017-5148-z

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