Sustainable Aromatic Copolyesters via Ring Opening Polymerization: Poly(butylene 2,5-furandicarboxylate-co-terephthalate)s

Abstract

A series of poly­(butylene 2,5-furan­dicarboxylate-co-terephthalate) copolyesters coPBF x T y covering the whole range of compositions has been prepared via ring opening polymerization (ROP). Cyclic oligomers of butylene 2,5-furan­dicarboxylate c(BF) n and butylene terephthalate c(BT) n , both mainly consisting of a mixture of dimer, trimer, and tetramer species, were synthesized by the high dilution condensation method. Random copolyesters with the targeted compositions and weight-average molecular weights within the 55 000–80 000 g·mol–1 range were obtained by ROP of c(BF) n /c(BT) n mixtures in periods of time much shorter than those required by melt polycondensation. The thermal properties of these copolyesters were consistent with their compositions and comparable to their isocompositional analogs obtained by polycondensation. A comparative kinetics study of the isothermal crystallization of the homopolyesters and copolyesters differing in composition revealed that the presence of the 2,5-furan­dicarboxylate units decreased the crystallization rate of PBT. Nevertheless, coPBF x T y copolyesters with moderate contents in BF units were still able to crystallized rapidly from the melt.

Organocatalyzed ring‐opening polymerization of cyclic butylene terephthalate oligomers

“…In addition, the fast kinetics observed for the entropically‐driven ROP of CBT, within minutes, enables a variety of techniques to be employed, such as reaction injection molding (RIM), resin transfer molding (RTM) or rotational molding (RM) . Complementary to their use as a precursor for thermoplastic matrix in composites, CBT has also been polymerized with the aim at producing nano‐composites, polymer blends, or copolymers …”

“…9 Complementary to their use as a precursor for thermoplastic matrix in composites, CBT has also been polymerized with the aim at producing nano-composites, 12,13 polymer blends, 14,15 or copolymers. 16,17 Because PBT shows high resistance to solvents, low moisture absorption and good mechanical properties at high temperature, it also represents an attractive candidate for the synthesis of thermoplastic elastomers. Nevertheless, only Chen et al have reported the synthesis of PBT-based triblock copolymers by ROP of CBT.…”

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

“…8 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. 13,14 Additionally, aromatic copolyesters made of butylene furanoate (BF) and butylene terephthalate (BT), 15 as well as aromatic-aliphatic copolyesters made from BF and butylene succinate (BS) 16 have been prepared by ROP in good yields with pretty high molecular weights. In these copolymerizations cyclic (BT) and (BS) oligomers were the respective Additional Supporting Information may be found in the online version of this article.…”

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

“…The interest in polymers derived from HMF and its derivatives has been rapidly increasing not only due to the sustainability and rich chemistry of HMF, but also due to the unique properties of these polymers. Currently, the preparation of HMF derivatives‐based polymers are mainly performed via chemical approaches . Enzymatic catalysis routes have been recently evaluated as well .…”

“…Currently, the preparation of HMF derivatives-based polymers are mainly performed via chemical approaches. 33,[121][122][123] Enzymatic catalysis routes have been recently evaluated as well. 53 Therefore, in this section, the synthesis and characterization of polymers via chemical methods will be reviewed, starting from three key monomers (FDCA, BHF, and DFF).…”