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Organocatalyzed ring opening polymerization of regio-isomeric lactones: reactivity and thermodynamics considerations

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Abstract

Organocatalysts are increasingly gaining attention for the ring opening polymerization (ROP) of lactones due to numerous advantages. In this work, the goal is to expand the scope of catalysts for the ROP of alkyl substituted caprolactones: a mixture of β,δ-trimethyl-ε-caprolactones (TMCL). Several organocatalysts were evaluated, with a focus on bifunctional organophosphorus catalysts including two novel categories, namely phosphonic acids and phosphinic acids. The effects of initial monomer concentration, temperature, catalyst loading and catalyst type on the monomer conversion at equilibrium and the reaction kinetics were addressed. The ceiling temperature of TMCL is 302 °C in bulk and 34 °C at 1 M, as determined experimentally. During polymerization, higher conversion and reaction rates were observed for the most substituted lactone (proximal lactone). This difference of reactivity between the two regio-isomeric lactones was greater for lower reaction temperatures. Density functional theory (DFT) calculations on the ring opening of the lactones demonstrated that the difference of reactivity can be attributed to a lower enthalpic contribution of the proximal lactone making the ring opening of this lactone more energetically favored. The difference in calculated Gibbs free energy was found to increase with lower temperature.

Graphical abstract: Organocatalyzed ring opening polymerization of regio-isomeric lactones: reactivity and thermodynamics considerations

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Article information


Submitted
25 Nov 2019
Accepted
02 May 2020
First published
05 May 2020

Polym. Chem., 2020, Advance Article
Article type
Paper

Organocatalyzed ring opening polymerization of regio-isomeric lactones: reactivity and thermodynamics considerations

M. A. F. Delgove, A. A. Wróblewska, J. Stouten, C. A. M. R. van Slagmaat, J. Noordijk, S. M. A. De Wildeman and K. V. Bernaerts, Polym. Chem., 2020, Advance Article , DOI: 10.1039/C9PY01777A

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