How the Aliphatic Glycol Chain Length Determines the Pseudoeutectic Composition in Biodegradable Isodimorphic poly(alkylene succinate- ran-caprolactone) Random Copolyesters

Biomacromolecules. 2024 Nov 11;25(11):7392-7409. doi: 10.1021/acs.biomac.4c01073. Epub 2024 Oct 21.

Abstract

We synthesize four series of novel biodegradable poly(alkylene succinate-ran-caprolactone) random copolyesters using a two-step ring-opening/transesterification and polycondensation process with ε-caprolactone (PCL) as a common comonomer. The second comonomers are succinic acid derivatives, with variations in the number of methylene groups (nCH2) in the glycol segment, nCH2 = 2, 4, 8, and 12. The obtained copolyesters were poly(ethylene succinate-ran-PCL) (ESxCLy), poly(butylene succinate-ran-PCL) (BSxCLy), poly(octamethylene succinate-ran-PCL) (OSxCLy), and poly(dodecylene succinate-ran-PCL) (DSxCLy). We discovered a new mixed isodimorphic/comonomer exclusion crystallization in ESxCLy copolymers. The BSxCLy, OSxCLy, and DSxCLy copolymers display isodimorphic behavior. Our findings revealed a significant variation in the pseudoeutectic point position, from mixed isodimorphism/comonomer exclusion crystallization to isodimorphism with pseudoeutectic point variation from 54% to up to 90%. Moreover, we established a link between the melting temperature depression slope variation and the comonomer inclusion/exclusion balance, providing valuable insights into the complex topic of isodimorphic random copolymers.

MeSH terms

  • Biocompatible Materials / chemistry
  • Caproates / chemistry
  • Crystallization
  • Glycols / chemistry
  • Lactones / chemistry
  • Polyesters* / chemistry
  • Polymers / chemistry
  • Succinates / chemistry

Substances

  • Polyesters
  • Lactones
  • caprolactone
  • Caproates
  • Succinates
  • Biocompatible Materials
  • Polymers
  • Glycols