Furan-2,5-Dicarboxylic Acid FDCA Based Polyesters

4 Furan-2,5-Dicarboxylic Acid (FDCA) Based Polyesters 

Storbeck and Ballauff were the first to report on polyesters based on FDCA and dianhydro-hexitols [16]. Here, the acid chloride of FDCA was reacted with all three dianhydrohexitol isomers, in 1,1,2,2-tetrachloroethane in the presence of pyridine, giving white, fibrous polyesters. This work has been discussed in detail in the preceding section on isohexide polyesters (section 9.2.2). Later, Gandini and co-workers performed some kinetic studies on the transesterification of the FDCA dimethyl ester [66-68]. However, little attention was paid to polymer properties. More recently a series of papers on FDCA polyesters has been published by various groups, indicating the renewed interest in this subject. 

Grosshardt et al. prepared a series of furan based polyesters, by reacting FDCA dimethyl ester with 1,3-propanediol, 1,6-hexanediol, 1,12-dodecanediol and 1,18-octadecanediol, using calcium acetate and antimony(III) oxide as catalysts [47]. Molecular weights and thermal properties were determined for all polyesters and are summarized in Table 9.6. 

Notes Measured by SEC, 70/20/10 (v/v/v) mixture of dichloromethane/chloroform/1,1,1,3,3,3-hexafluoro2-propanol (HFIP) 70/20/10 was used as the eluent, compared to polystyrene [17]. Measured by elemental analysis after hydroxyl end-group functionalization with pentafluorobenzoyl chloride [17]. Measured by SEC, HFIPaseluent, compared to polymethylmethacrylate [49. Measured by SEC, HFIP as eluent, compared to polymethylmethacrylate [471. Ref. 170). Refs. 14, 34, 70.  

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Another class of interesting isohexide polyesters contains furan-2,5-dicarboxylic acid (2,5-FDA or FDCA, Figure 9.5) as the aromatic diacid component. Since FDCA can be obtained from carbohydrates via various routes, this opens up possibilities for fully bio-based semiaromatic polyesters. 

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