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

Macromol Rapid Commun. 2017 Feb;38(4). doi: 10.1002/marc.201600638. Epub 2017 Jan 3.

Abstract

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.

Keywords: Candida antarctica lipase B; aliphatic polymacrolactones; all-aliphatic polyester material properties; enzymatic ring-opening polymerization; macrocyclic monolides.

MeSH terms

  • Fungal Proteins / chemistry
  • Fungal Proteins / metabolism*
  • Lactones / chemistry
  • Lactones / metabolism*
  • Lipase / chemistry
  • Lipase / metabolism*
  • Molecular Structure
  • Polyesters / chemistry
  • Polyesters / metabolism*
  • Polymerization*

Substances

  • Fungal Proteins
  • Lactones
  • Polyesters
  • Lipase
  • lipase B, Candida antarctica