Homopolymerization and copolymerization of a dilactone, 13,26‐dihexyl‐1,14‐dioxa‐cyclohexacosane‐2,15‐dione: Synthesis of bio‐based polyesters and copolyesters consisting of 12‐hydroxystearate sequences

Abstract

A dilactone, 13,26‐dihexyl‐1,14‐dioxacyclohexacosane‐2,15‐dione (12‐HSAD), was synthesized by lipase‐catalyzed reaction of 12‐hydroxystearic acid (12‐HSA) in high yield. It was subjected to the ring‐opening polymerization with various catalysts to obtain poly(12‐hydroxystearate) (PHS). The polymerization system of 12‐HSAD showed an interesting polymerization behavior because of its large ring system. The polymers produced by this polymerization were directly reacted with L‐lactide to obtain a diblock copolymer of poly(L‐lactide)‐block‐poly‐(12‐hydroxystearate) (PLLA‐b‐PHS). Characterization of the resultant copolymers was also performed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Kinetic Investigation on the Catalytic Ring-Opening (Co)Polymerization of (Macro)Lactones Using Aluminum Salen Catalysts

“…The catalytic ring-opening polymerization ( c ROP) of macrolactones to polymacrolactones (PMLs) has great potential since this route allows the formation of high molecular weight products, which possess good ductility and strength, similar to polyethylene (PE) and in contrast to other renewable polymers such as PLA and polyhydroxyalkanoates (PHAs) that are intrinsically brittle. ,− Due to the living or even immortal character of most of the c ROP catalysts and their tolerance to a wide variety of functional groups, random-, alternating-, block-, gradient-, and graft-copolymers with tunable molecular weight can be synthesized using for example (di)lactones, cyclic carbonates or the combination of epoxides and CO 2 or anhydrides. ,− In this they outperform enzymes, which give high molecular weight PMLs but show poor control over the polymer microstructure as the transesterification mechanism exclusively yields random copolyesters. ,,− …”