The first example of solvent-free, organocatalyzed, polymerization of 1,3-dioxolan-4-ones, used as easily accessible monomers for the synthesis of polylactic acid (PLA), is described here. An optimization of reaction conditions was carried out, with p-toluensulfonic acid emerging as the most efficient Brønsted acid catalyst. The reactivity of the monomers in the tested conditions was studied following the monomer conversion by1H NMR and the molecular weight growth by SEC analysis. A double activation polymerization mechanism was proposed, pointing out the key role of the acid catalyst. The formation of acetal bridges was demonstrated, to different extents depending on the nature of the aldehyde or ketone employed for lactic acid protection. The polymer shows complete retention of stereochemistry, as well as good thermal properties and good polydispersity, albeit modest molecular weight.

1,3-dioxolan-4-ones as promising monomers for aliphatic polyesters : Metal-free, in bulk preparation of PLA / S. Gazzotti, M.A. Ortenzi, H. Farina, A. Silvani. - In: POLYMERS. - ISSN 2073-4360. - 12:10(2020), pp. 2396.1-2396.14. [10.3390/polym12102396]

1,3-dioxolan-4-ones as promising monomers for aliphatic polyesters : Metal-free, in bulk preparation of PLA

S. Gazzotti
;
M.A. Ortenzi;H. Farina;A. Silvani
Ultimo
2020

Abstract

The first example of solvent-free, organocatalyzed, polymerization of 1,3-dioxolan-4-ones, used as easily accessible monomers for the synthesis of polylactic acid (PLA), is described here. An optimization of reaction conditions was carried out, with p-toluensulfonic acid emerging as the most efficient Brønsted acid catalyst. The reactivity of the monomers in the tested conditions was studied following the monomer conversion by1H NMR and the molecular weight growth by SEC analysis. A double activation polymerization mechanism was proposed, pointing out the key role of the acid catalyst. The formation of acetal bridges was demonstrated, to different extents depending on the nature of the aldehyde or ketone employed for lactic acid protection. The polymer shows complete retention of stereochemistry, as well as good thermal properties and good polydispersity, albeit modest molecular weight.
1,3-dioxolan-4-one; Brønsted acid; Lactide; Organocatalysis; PLA
Settore CHIM/06 - Chimica Organica
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/792705
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