Poly(alkylene 2,5-furandicarboxylate)s (PEF and PBF) by ring opening polymerization

• Published in: Polymer (Guilford) 2016-03, Vol.87, p.148-158
• Main Authors: Morales Huerta, Juan Carlos, Martínez de Ilarduya Sáez de Asteasu, Domingo Antxon, Muñoz Guerra, Sebastián
• Format: Article
• Language: English
• Subjects: 5-furandicarboxylate)s; Bio-based aromatic polyesters; Condensation; Conversion; Crystal structure; Cyclic oligoesters; Enginyeria química; entropically driven ring opening polymerization; Ethylene; Melting; Melts; PBF; PEF; Polimerització; Polièsters; poly(alkylen 2; Polyester resins; Polyesters; Polyfuranoates; Polymerization; Ring opening polymerization; ROP; Àrees temàtiques de la UPC
• ISSN: 0032-3861; 1873-2291
• DOI: 10.1016/j.polymer.2016.02.003

The preparation of cyclic ethylene and butylene 2,5-furandicarboxylate oligoesters and their conversion to furan-based polyesters poly(ethylene furanoate) (PEF) and poly(butylene furanoate) (PBF) by ring-opening polymerization (ROP) are described. The cyclic oligoesters were obtained in high yields by both high dilution condensation and thermal cyclodepolymerization methods, and they consisted of mixtures of small size species. Cyclic dimer, trimer and tetramer oligoesters were isolated by semipreparative chromatography and found to be crystalline compounds melting within the 140–200 °C range. ROP catalyzed by Sn(Oct)2 of both mixtures and individual species afforded PEF and PBF with weight-average molecular weights between 50,000 and 60,000 g mol−1. Polymerization rate was found to be higher for butylene than for ethylene cyclic oligofuranoates, and also to increase slightly as cycle size decreased. The thermal properties of PEF and PBF prepared by ROP were in full agreement with those reported for these polyesters obtained by melt polycondensation. [Display omitted] •Cyclic oligoesters of BF and EF were prepared in high yields by both high-dilution and thermal cyclodepolymerization methods.•PBF and PEF were successfully synthesized by ring opening polymerization catalyzed by tin octanoate.•Ring opening polymerization is a suitable option for the synthesis of poly(alkylene furanoate)s.