Fast organocatalytic ring-opening polymerization of aliphatic glycolides: structure–property relationships in tunable homopolymers


Çetin D., Karaşahin S., Tutuş B., Duruksu G., Arıcan M. O., Asri H., ...Daha Fazla

European Polymer Journal, cilt.255, 2026 (SCI-Expanded, Scopus)

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 255
  • Basım Tarihi: 2026
  • Doi Numarası: 10.1016/j.eurpolymj.2026.114890
  • Dergi Adı: European Polymer Journal
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Chemical Abstracts Core, Chimica, Compendex, INSPEC, Academic Search Ultimate (EBSCO), Engineering Source (EBSCO)
  • Anahtar Kelimeler: Catalyst bifunctionality, Degradable Polymers, Sterically hindered monomers
  • Kocaeli Üniversitesi Adresli: Evet

Özet

Developing rapid and controlled organocatalytic ring-opening polymerization (ROP) for aliphatic lactide and glycolide monomers is critical for advancing polyester materials. Here, we demonstrate the exceptional catalytic performance of a series of organic superbases to achieve fast and well-controlled polymerizations under mild conditions. Polymerizations proceeded at room temperature and reached completion within 5 min, affording poly(alkyl lactide/glycolide) homopolymers with high conversions (≥96%) and isolated yields up to 86%. TBD exhibited the highest catalytic activity, attributed to its bifunctional structure and strong Brønsted basicity, whereas DBN showed the lowest reactivity. Controlled polymerization was demonstrated by the linear increase in molecular weights with increasing monomer-to-initiator ratios and narrow dispersity indices (ĐM = 1.13–1.14), particularly under MTBD catalysis. Thermal analysis confirmed the amorphous nature of all polymers, with glass transition temperatures (Tg) decreasing systematically as the alkyl side-chain length increased, ranging from 27.0 °C (PEL) to 4.2 °C (PBuL) and from 4.4 °C (PPEG) to –5.5 °C (PBEG). In vitro cytocompatibility assays using NIH-3 T3 fibroblasts revealed excellent biocompatibility, with cell viability remaining above 90% for all polymers at concentrations up to 15.5 µg/mL. Incorporation of polymers into the culture media caused no significant cytotoxic effects, irrespective of polymer identity. These results demonstrate the potential of fast organocatalytic ROP for the synthesis of structurally diverse and biocompatible polyesters. The synthesized poly(alkyl lactide/glycolide) homopolymers offer promising alternatives to conventional PLA and PLGA materials for biomedical applications.