No Strain, No Gain? Enzymatic Ring‐Opening Polymerization of Strainless Aliphatic Macrolactones

Starting from readily available oleic and erucic acid, macrocyclic nonadecalactone (C19) and tricosalactone (C23) can be synthesized in polymerization grade purity in a four‐step reaction sequence. Ring‐opening polymerization (ROP) of these strainless macrolactones can be performed utilizing an enzyme as a catalyst. Despite the missing ring‐strain as key driving force for smaller (strained) lactones, high molar masses (Mn ≈ 105 g mol−1) can be accessed in an entropically driven ROP. Polyester‐19 and polyester‐23 prepared feature melting temperatures well above 100 °C. Further analysis of the mechanical properties of these materials displays the resemblance to polyethylene. For example, Young's moduli on the order of 600 MPa are observed as a result of the high crystallinity of the polymer. Macrolactones containing a C19 and C23 hydrocarbon segment can be accessed from plant oils in a four‐step reaction sequence. Enzymatic entropy‐driven ring‐opening polymerization of these strainless macrolactones yields high‐molar‐mass polyesters. Furthermore, investigation of the mechanical properties is presented, showing similarities to polyethylene.