The Mechanisms of the Initiation Step in Ring-Opening Polymerization of β-Lactones: A Review

Ring-opening polymerization (ROP) of β-lactones yields biodegradable and bioresorbable polyesters exhibiting potential utility in medicine and environmental protection. β-butyrolactone (BL) is especially interesting, as it yields polymers analogous to natural poly(3-hydroxybutyrates) produced by bacteria, fungi, and enzymes in nature. The biopolymer produced by these microorganisms is isotactic. While it can be synthesized biotechnologically through the bacterial fermentation of substrates, such as sucrose, corn, and sugar, laboratory production typically involves the ring-opening polymerization of BL. However, the latter process is mainly atactic, syndiotactic, or partly isotactic, and other β-substituted β-lactones are less well-known. Ring-opening polymerization is an excellent pathway for the production of poly(β-lactones). This critical review presents the different conditions required to synthesize poly(β-lactones) and a broad overview of the different kinds of ROPs, i.e., anionic, cationic, coordinative, supramolecular-based, and enzymatic processes. A great variety of initiators/catalysts have been studied, covering both metal-based and metal-free systems (organo- and biocatalysts). In this review, several mechanisms of β-lactone polymerization are presented and discussed, especially with regard to the processes’ initiation steps.