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Theoretical investigation on the mechanism and kinetics of the ring-opening polymerization of ε-caprolactone initiated by tin(II) alkoxides

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Abstract

A theoretical investigation of the ring-opening polymerization (ROP) mechanism of ε-caprolactone (CL) with tin(II) alkoxide, Sn(OR)2 initiators (R = n-C4H9, i-C4H9, t-C4H9, n-C6H13, n-C8H17) was studied. The density functional theory at B3LYP level was used to perform the modeled reactions. A coordination-insertion mechanism was found to occur via two transition states. Starting with a coordination of CL onto tin center led to a nucleophilic addition of the carbonyl group of CL, followed by the exchange of alkoxide ligand. The CL ring opening was completed through classical acyl-oxygen bond cleavage. The reaction barrier heights of ε-caprolactone with different initiators were calculated using potential energy profiles. The reaction of ε-caprolactone with Sn(OR)2 having R = n-C4H9 has the least value of barrier height compared to other reactions. The rate constants for each reaction were calculated using the transition state theory with TheRATE program. The rate constants are in good agreement with available experimental data.

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Acknowledgments

The authors wish to thank the National Research University Project under Thailand’s Office of the Higher Education Commission for financial support and National Science and Technology Development Agency (NSTDA). C. Sattayanon gratefully thanks the Center for Innovation in Chemistry (PERCH-CIC), Department of Chemistry, Faculty of Science, Chiang Mai University. And the Graduate School of Chiang Mai University is also acknowledged.

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Authors and Affiliations

  1. Center of Excellence for Innovation in Chemistry, Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai, Thailand, 50200

    Chanchai Sattayanon, Nawee Kungwan, Winita Punyodom & Puttinan Meepowpan

  2. Biomedical Polymers Technology Unit, Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai, Thailand, 50200

    Nawee Kungwan, Winita Punyodom & Puttinan Meepowpan

  3. Center for Organic Electronic and Alternative Energy, Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani, Thailand, 34190

    Siriporn Jungsuttiwong

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  1. Chanchai Sattayanon
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  2. Nawee Kungwan
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  3. Winita Punyodom
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  4. Puttinan Meepowpan
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Correspondence to Nawee Kungwan.

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Sattayanon, C., Kungwan, N., Punyodom, W. et al. Theoretical investigation on the mechanism and kinetics of the ring-opening polymerization of ε-caprolactone initiated by tin(II) alkoxides. J Mol Model 19, 5377–5385 (2013). https://doi.org/10.1007/s00894-013-2026-2

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  • DOI: https://doi.org/10.1007/s00894-013-2026-2

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