Copolymerization of β‐Butyrolactones into Functionalized Polyhydroxyalkanoates Using Aluminum Catalysts: Influence of the Initiator in the Ring‐Opening Polymerization Mechanism

Author:

Palenzuela Miguel1,Mula Esther1,Blanco Carlos1,Sessini Valentina1,Shakaroun Rama M.2,Li Hui2,Guillaume Sophie M.2ORCID,Mosquera Marta E. G.1ORCID

Affiliation:

1. Departamento de Química Orgánica y Química Inorgánica, Instituto de Investigación en Química “Andrés M. del Río” (IQAR), Universidad de Alcalá Campus Universitario Alcalá de Henares Madrid 28871 Spain

2. Univ. Rennes, CNRS Institut des Sciences Chimiques de Rennes UMR 6226 Rennes F‐35042 France

Abstract

AbstractWithin 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 [AlMeL2], 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.

Funder

Comunidad de Madrid

Universidad de Alcalá

Ministerio de Ciencia, Innovación y Universidades

Publisher

Wiley

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