Preparation of Poly(ether ketone)s Derived from 2,5-Furandicarboxylic Acid by Polymerization in Ionic Liquid

Abstract

Aromatic poly(ether ketone)s were synthesized by the Friedel−Crafts polymerization of 2,5-furandicarbonyl dichloride prepared from biomass and petroleum-based aromatic ethers such as diphenyl ether and 1,4-diphenoxybenzene with aluminum chloride (AlCl 3 ). The polymerizations in common molecular solvents such as 1,2-dichloroethane and nitrobenzene did not afford polymers. The Friedel−Crafts polymerization usually undergoes in the swollen gel of the oligomer−AlCl 3 complexes; the precipitated physical gels had not been enough swollen. The polymerizations were carried out in various ionic liquids to form swollen gels. The polymerizations proceeded in specific ionic liquid such as 1-butyl-3-methylimidazolium chloride ([C 4 mim]Cl), and high molecular weight polymers were obtained with good yield. The gels formed in [C 4 mim]Cl were more highly swollen, and additionally the rate constant estimated by the model reaction of 2,5furandicarbonyl dichloride and anisole was higher in [C 4 mim]Cl than that in 1,2-dichloroethane. The obtained poly(ether ketone)s exhibited good thermal stability and chemical resistance comparable to common poly(ether ketone)s.

Preparation of poly(ether ketone)s derived from 2,5‐furandicarboxylic acid via nucleophilic aromatic substitution polymerization

“…It was the same polymer structure as F‐PEEKK(HQ) prepared in this study. T m of F‐PEEKK(HQ′) was 216 °C, which was much lower than that of F‐PEEKK(HQ). In case of the electrophilic aromatic substitution reaction, FDCC reacted with p ‐position carbons to the ether linkage of 1,4‐diphenoxybenzene mainly, but it did often with o ‐position carbons to ether linkage.…”

“…T g of F‐PEEKK(HQ) and F‐PTTKK(TBT) could not be detected with changing scanning rate of DSC measurements. F‐PEEKK (F‐PEEKK(HQ′)) had been prepared by the electrophilic aromatic substitution polymerization of FDCC and 1,4‐diphenoxybenzene . It was the same polymer structure as F‐PEEKK(HQ) prepared in this study.…”

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).…”

Synthesis of Poly(ether ketone)s from 2,5-Thiophenedicarboxylic Acid

“…In our previous work [3], PEKs containing furan-ring (F-PEK) were prepared from 2,5-furandiacarbonyl dichloride (FDCC) and aromatic ethers by aromatic electrophilic substitution polymerization so-called Friedel-Crafts polymerization. The polymerizations of FDCC and the aromatic ethers in molecular solvents such as 1,2-dichloroethane (DCE) and nitrobenzene which were common solvents for the polymerizations did not yield the high molecular weight PEKs because of the low affinity of precipitated physical gels among solvent, catalyst and the oligomers.…”