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

Abstract

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.Peer ReviewedPostprint (author's final draft

Blocky poly(ɛ‐caprolactone‐co‐butylene 2,5‐furandicarboxylate) copolyesters via enzymatic ring opening polymerization

“…The cyclic oligomers c (BF) n used for copolymerization with CL were prepared by applying the high‐dilution condensation method recently reported by us . Copolymerization of CL with c (BF) n was performed in bulk using CALB as catalyst.…”

“…After removing the enzyme by filtration, the solvent was evaporated under vacuum and the solid residue was dried for 24 h before analysis. PCL homopolyester was obtained from CL by the same procedure whereas the synthesis of PBF was performed by cyclopolymerization of c (BF) n catalyzed by TBT as previously described by us …”

“…PEF and PBF are usually prepared by polycondensation of FDCA or its dimethyl ester (FDCA‐Me 2 ) with ethylene glycol and 1,4‐butanediol (BD), respectively . However the access to cyclic (alkylene 2,5‐furandicarboxylate) oligomers [ c (EF) n and c (BF) n ] recently afforded by chemical synthesis has opened the ROP route toward the preparation of these polyesters . Additionally, aromatic copolyesters made of butylene furanoate (BF) and butylene terephthalate (BT), as well as aromatic‐aliphatic copolyesters made from BF and butylene succinate (BS) have been prepared by ROP in good yields with pretty high molecular weights.…”

Advances in polymer precursors and bio‐based polymers synthesized from 5‐hydroxymethylfurfural

“…However, issues still exist, such as a long reaction time (hours to days) required to attain high reaction extents, and poor mass and heat transfer when the melt viscosity was high. Other synthesis routes, such as direct esterification using tetrabutyl titanate as a catalyst, ring opening polymerization of cyclic FDCA‐based monomers, and the combination of melting polymerization and subsequent solid state post condensation, have also been presented. For the ring opening polymerization, although PEF with weight‐average molecular weight between 50,000 and 60,000 g/mol has been synthesized, the complicated process for the preparation of cyclic monomer and relatively low yield might limit its application.…”

Catalytic Ring-Opening (Co)polymerization of Semiaromatic and Aliphatic (Macro)lactones

“…35,36 More recently, also poly(ethylene furandicarboxylate) and poly(butylene furandicarboxylate) have been obtained via ROP. 37 Among the semiaromatic macrolactones, the ROP of cyclic butylene terephthalate (cBT) has been studied most intensively. 19 Cyclic butylene terephthalate oligomers are commercially available and more easily produced compared to their PET counterpart, and they can be used for reactive injection molding of (nano)composite structures, 31,33,34,38,39 as processing aid, and as additive carrier.…”