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Kinetics and thermodynamics studies of the ring-opening polymerization of ε-caprolactone initiated by titanium(IV) alkoxides by isothermal differential scanning calorimetry

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Abstract

The structure–reactivity relationship of titanium(IV) alkoxides (Ti(OR)4; R = n-propoxide, n-butoxide, tert-butoxide and 2-ethylhexoxide) in the ring-opening polymerization of ε-caprolactone (ε-CL) has been successfully investigated by differential scanning calorimetry (DSC) technique. Based on isothermal method, the kinetic results demonstrated that the polymerization rate decreased with increasing chain length and bulkiness of alkoxy group of Ti(OR)4. The determined activation energy (Ea) from autocatalytic model (f(α) = αm(1 − α)n) for titanium(IV) n-propoxide, n-butoxide, tert-butoxide and 2-ethylhexoxide were found to be 77.7, 97.2, 105.2 and 97.9 kJ/mol. From thermodynamics analysis of transition state (TS) formulation, the obtained activation enthalpy (∆H≠) values revealed that the titanium(IV) n-propoxide required the lowest energy to form the TS with ε-CL. From the obtained activation entropy (∆S≠) values, it was found that the stability of TS of ε-CL with titanium(IV) n-propoxide was higher than n-butoxide, 2-ethylhexoxide and tert-butoxide. From the overall results, it is clearly indicated that the steric hindrance of Ti(OR)4 initiators plays an important role on the kinetics and thermodynamics of polymerization process. The reactivity of Ti(OR)4 initiators was determined in the order of: titanium(IV) n-propoxide > n-butoxide ≈ 2-ethylhexoxide > tert-butoxide. The polymerization mechanism of all Ti(OR)4 initiators with ε-CL was proposed through the coordination-insertion mechanism.

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adapted from literature [19]

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Acknowledgements

The authors wish to thanks the financial supports from Chiang Mai University (WP and PM), the Thailand Research Fund (TRF) (MRG6080164) (WL) and Office of the Higher Education Commission (OHEC) (WL). The Department of Chemistry and Materials Science Research Center, Faculty of Science, Chiang Mai University, Faculty of Sciences and Agricultural Technology, Rajamangala University of Technology Lanna and University of Phayao are also acknowledged.

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Authors and Affiliations

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

    Wanich Limwanich

  2. Division of Chemistry, School of Science and Demonstration School, University of Phayao, Phayao, 56000, Thailand

    Wijitra Meelua

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

    Puttinan Meepowpan & Winita Punyodom

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

    Puttinan Meepowpan & Winita Punyodom

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  1. Wanich Limwanich
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  2. Wijitra Meelua
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  4. Winita Punyodom
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Correspondence to Winita Punyodom.

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Limwanich, W., Meelua, W., Meepowpan, P. et al. Kinetics and thermodynamics studies of the ring-opening polymerization of ε-caprolactone initiated by titanium(IV) alkoxides by isothermal differential scanning calorimetry. Reac Kinet Mech Cat 135, 881–895 (2022). https://doi.org/10.1007/s11144-022-02184-z

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