Sustainable Hyperbranched Functional Materials via Green Polymerization of Readily Accessible Levoglucosenone‐Derived Monomers

• Published in: Macromolecular rapid communications. 2021-10, Vol.42 (19), p.e2100284-n/a
• Main Authors: Fadlallah, Sami, Flourat, Amandine L., Mouterde, Louis M. M., Annatelli, Mattia, Peru, Aurélien A. M., Gallos, Antoine, Aricò, Fabio, Allais, Florent
• Format: Article
• Language: English
• Subjects: Accessibility; Chemical Sciences; Copolymers; Environmental factors; Functional materials; green polymerization; HBO; hyperbranched materials; levoglucosenone; Monomers; Polymerization; Polymers; renewable polymers
• ISSN: 1022-1336; 1521-3927
• DOI: 10.1002/marc.202100284

The homopolymerization in basic conditions of the recently reported bis(γ‐lactone), 2H‐HBO‐HBO, is herein described for the first time. The solvent‐free polymerization of this pentafunctional levoglucosenone (LGO) derivative affords fully renewable poly(vinyl‐ether lactone) copolymers with a highly hyperbranched structure. This investigation stems from the polycondensation trials between 2H‐HBO‐HBO and di(methyl carbonate) isosorbide (DCI) that fails to give the anticipated polycarbonates. Such unexpected behavior is ascribed to the higher reactivity of the 2H‐HBO‐HBO hydroxy groups toward its α,β‐conjugated endocyclic C═C, rather than the DCI methylcarbonate moieties. The different mechanistic scenarios involved in 2H‐HBO‐HBO homopolymerization are addressed and a possible structure of poly(2H‐HBO‐HBO) is suggested. Furthermore, the readily accessible (S)‐γ‐hydroxymethyl‐α,β‐butenolide (HBO) is also polymerized for the first time at a relatively large scale, without any prior modification, resulting in a new hyperbranched polymer with an environmental factor (E factor) ≈0. These new HBO‐based polymers have a great potential for industrial‐scale production due to their interesting properties and easy preparation via a low‐cost, green, and efficient process. The environmentally benign polymerization of (S)‐γ‐hydroxymethyl‐α,β‐butenolide (HBO) and bis(γ‐lactone) (2H‐HBO‐HBO), which are readily accessible from cellulose byproducts, leads to the formation of 100% renewable poly(vinyl‐ether lactone) copolymer structures. The easiness of preparation of these HBO‐based polymers, their low‐cost production process, as well as their interesting and tunable thermal properties, make them a suitable choice to substitute petrochemical‐derived commodity polymers.