1. Copolymerization of β-Butyrolactones into Functionalized Polyhydroxyalkanoates Using Aluminum Catalysts: Influence of the Initiator in the Ring-Opening Polymerization Mechanism.
- Author
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Palenzuela M, Mula E, Blanco C, Sessini V, Shakaroun RM, Li H, Guillaume SM, and Mosquera MEG
- Subjects
- Catalysis, Molecular Structure, Hydroxybutyrates chemistry, Polyhydroxybutyrates, Polymerization, 4-Butyrolactone chemistry, 4-Butyrolactone analogs & derivatives, Polyhydroxyalkanoates chemistry, Aluminum chemistry
- Abstract
Within bioplastics, natural poly(3-hydroxybutyrate) (PHB) stands out as fully biocompatible and biodegradable, even in marine environments; however, its high isotacticity and crystallinity limits its mechanical properties and hence its applications. PHB can also be synthesized with different tacticities via a catalytic ring-opening polymerization (ROP) of rac-β-butyrolactone (BBL), paving the way to PHB with better thermomechanical and processability properties. In this work, the catalyst family is extended based on aluminum phenoxy-imine methyl catalyst [AlMeL
2 ], that reveals efficient in the ROP of BBL, to the halogeno analogous complex [AlClL2 ]. As well, the impact on the ROP mechanism of different initiators is further explored with a particular focus in dimethylaminopyridine (DMAP), a hardly studied initiator for the ROP of BBL. A thorough mechanistic study is performed that evidences the presence of two concomitant DMAP-mediated mechanisms, that lead to either a DMAP or a crotonate end-capping group. Besides, in order to increase the possibilities of PHB post-polymerization functionalization, the introduction of a side-chain functionality is explored, establishing the copolymerization of BBL with β-allyloxymethylene propiolactone (BPLOAll ), resulting in well-defined P(BBL-co-BPLOAll ) copolymers., (© 2024 The Authors. Macromolecular Rapid Communications published by Wiley‐VCH GmbH.)- Published
- 2024
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