Dianhydrohexitols based Polymers

The use of polymers from renewable 1,4,3,6-dianhydrohexitols has been reviewed (34,35). Isosorbide, isomannide, and isoidide are basically stereo isomers from dianhydrohexitol compounds. 

Isosorbide derivates are of considerable importance for the replacement of fossil resource-based products. Applications include building blocks for new polymers and functional materials, new organic solvents, for medical and pharmaceutical applications, as weU as fuels (36). The derivatization of isosorbide is somewhat problematic because of the different configurations of the 2- and 5-positions and thus of the different reactivity of the hydroxyl groups. 

In general, hydroxyethylation processes with ethylene carbonate generally result in a mixture of products. The initially formed bis(2-hydroxyethyl)isosorbide may further react with ethylene carbonate to form higher hydroxy terminated polyethers. The formation of such higher polyethers may be controlled by the amoimt of added ethylene carbonate, and the nature of the catalyst system (37). Further, the raw bis(2-hydroxyethyl)isosorbide may be purified by distillation. 

Isosorbide is used for medical applications, such as a diuretic agent and can be also used for the treatment of eye diseases to decrease the fluid pressure in the eye. 

Eventually, bis(2-hydroxyethyl)isosorbide may be chemically modified to form, bisacrylate esters or bis vinyl ethers, which can be used in photochemical or thermal cured vinyl resin compositions. Alternatively, this compound may be reacted with epichlorohy-drin and bases to form bis(glycidyl ether) adducts which may be used in epoxy resins. Bis(2-hydroxyethyl)isosorbide will find use as a monomer in many polymeric compositions, such as polyesters, poly(urethane)s, poly(ether sulfone)s. 

---

In addition, isosorbide and other l,4 3,6-dianhydrohexitols (isomannide derived from D-mannose, isoidide derived from L-fructose) are also attractive to serve as monomers for polymer production due to their rigidity, chirality, and non-toxicity (Fig. 6). Such features may introduce special properties into the polymers formed, such as enhanced Jg and/or special optical properties. Their innocuous nature also opens the possibility of applications in packaging or medical devices. As a bifunctional monomer, isosorbide can be polymerized with other bifunctional monomers via condensation polymerization. A recent review described various isosorbide-based polymers synthesized, including polyesters, polyamides, poly(ester amide)s, poly(ester imide)s, polycarbonates, polyurethanes, and so on [308], and the present... 

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. 

Okada, M., Okada, Y, Tao, A. and Aoi, K. (1996) Biodegradable polymers based on renewable resources polyesters composed of 1,4 3,6-dianhydrohexitol and aliphatic dicarboxylic acid units. Journal of Applied Polymer Science, 62 (13), 2257-2265. 

Yokoe M., Aoi K., Okada M., Biodegradable polymers based on renewable resources. Vll. Novel random and alternating copolycarbonates from l,4 3,6-dianhydrohexitols and aliphatic diols, J. Polym. ScL Part A Polym. Chem., 41,2003,2312-2321. Yokoe M., Aoi K., Okada M., Biodegradable polymers based on renewable resources. Vlll. Environmental and enzymatic degradabihty of copolycarbonates containing l,4 3,6-dianhydrohexitols, J. App. Polym. ScL, 98, 2005,1679-1687. 

Storbeck R, Ballauff M (1993) Synthesis and properties of polyesters based on 2,5-furandicarboxylic acid and l,4/3,6-dianhydrohexitols. Polymer 34(23) 5003-5006 Thomas SM, DiCosimo R, Nagarajan A (2002) Biocatalysis applications and potentials for the chemical industry. Trends Biotechnol 20(6) 238-242 Ugidos A, Morales G, Rial E, Williams HD, Rojo F (2008) The coordinate regulation of multiple terminal oxidases by the Pseudomonas putida ANR global regulator. Environ Microbiol 10 (7) 1690-1702... 

---