Polyamides 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. 

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... 

Linear, high molecular weight polyamides were obtained when aliphatic, aromatic, and heterocyclic diamines were reacted with aromatic and heterocyclic ortho-dicarboxylic acid dichlorides. Interfacial polymerization of an aqueous, alkaline solution of trans-2,5-dimethyIpiperazine with 3,4-furan dicarbonyl chloride in methylene chloride produced a polyamide in 97% yield with inherent viscosity of 3.71 in H SO. The polymer exhibited good stability to heat and hydrolysis and a glass transition temperature... 

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