Polyesters furan dicarboxylic acid

Moore, J.A. and Bunting, W.W. (1985) Polyesters and polyamides containing isomeric furan dicarboxylic acids. Polymer Scienceand Technology, Advanced Polymer Synthesis, 31, 51-91. 

A considerable amount of work has been done using furan, J[, derivatives to synthesize polyesters, polyamides, and various other polymeric mater-ials. Much of this work has been completed in the last thirty years, with the majority of it dealing with 2,5-furan dicarboxylic acid and its derivatives. 2,4-Furan dicarboxylic acid, and 3,4-furan dicarboxylic acid, and their derivatives have been less used as starting materials. Little or no polymer synthesis has been reported employing 2,3-furan dicarboxylic... 

Considering these differences, it is the purpose of this work to synthesize representative polyesters and polyamides which incorporate derivatives of the four isomeric furan dicarboxylic acids, and to determine if these polymers bear any relationship in properties to similar polymers derived from benzene. Similarity in basic position and distance between carboxyl groups may permit examination and ordering of poljnners containing the isomeric benzene diacids. Some comparisons are shown below. 

The diacids necessary for this work were 2,5-furan dicarboxylic acid, 2, 2,4-furan dicarboxylic acid, 4, 3,4-furan dicarboxylic acid, 5, and 2,3-furan dicarboxylic acid, 6. These compounds were prepared by literature procedures and/or purchased (Aldrich Chemical Co.) and then converted to the respective diacid chlorides to prepare polyesters and polyamides. 

Most of these furan polycondensates are more sensitive to thermal and oxidative degradation than their benzene counterparts. Particularly affected are the polyesters obtained from 2,5 -fci sfhydroxymethyl) furan indicating that one of the vulnerable groups must be the -Fu—CH2—0-, and not the -Fu—CO—O-, since polycondensates obtained from 2,5-dicarboxylic acid are more stable, as expected from the... 

The hydrogenation of HMF in the presence of metal catalysts (Raney nickel, supported platinum metals, copper chromite) leads to quantitative amounts of 2,5-bis(hydroxymethyl)furan used in the manufacture of polyurethanes, or 2,5-bis(hydroxymethyl)tetrahydrofuran that can be used in the preparation of polyesters [30]. The oxidation of HMF is used to prepare 5-formylfuran-2-carboxylic acid, and furan-2,5-dicarboxylic acid (a potential substitute of terephthalic acid). Oxidation by air on platinum catalysts leads quantitatively to the diacid. [32], The oxidation of HMF to dialdehyde was achieved at 90 °C with air as oxidizing in the presence of V205/Ti02 catalysts with a selectivity up to 95% at 90% conversion [33]. 

Furan-2,5-dicarboxylic add also has tremendous industrial potential, because it could replace oil-derived diadds such as adipic or terephthalic acid as monomers for polyesters and polyamides [98, 99]. This diadd can be synthesized by Pt-catalyzed oxidation with 02 of 5-hydroxymethylfurfural the latter is obtained by acid-catalyzed dehydration of D-frudose or frudosans (inulin) the latter, however, are too expensive as starting materials, and yields from glucose-based waste raw materials are no higher than 40%. Therefore, the potential attractive option of furan-2,5-dicarboxylic acid will develop only after an effident generation of 5-hydroxymethylfurfural from forestry waste materials has been developed. The same compound is also the starting material for the synthesis of other interesting chemicals obtained by oxidative processes, such as 5-hydroxymethylfuroic add, 5-formylfuran-2-carboxylic add and the 1,6-dialdehyde. 

Bis(hydroxymethyl) furan and 5-hydroxymethyl furfural (available from C6 sugars) have been oxidized to furan-2,5-dicarboxylic acid (44)- Linear polyesters, polyurethanes, and polyamides containing these monomers have been described in the literature (45-43) and have been made via condensation polymerization techniques including bulk, solution, and interfacial mixing procedures. Gandini (5,34) reviewed the poly condensation reactions up to 1986 and... 

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. 

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

In 1975, Kellyprepared and characterized a number of polyesters based on 2,5-disubstituted furans in various states of reduction. In this study, 2,5-disubstituted-furan, -dihydrofuran, and -tetrahydrofuran monomers were polymerized using solution, melt-transesterification, ring-opening, and interfacial techniques. These monomers included diacids, diols, diacid chlorides, diesters, dicarboxylic acid anhydrides, as well as monomers based on 5-hydroxymethyl-2-furoic and tetrahydrofuroic acids and esters, and bycyclic lactones containing the tetrahydrofuran ring. A thorough review of previous work done in the area of poljnner synthesis, based on 2,5-disubstituted furan derivatives is reported. It is reported that when... 

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