9.2 2,5-Furan dicarboxylic acid (FDCA) 9.2.1 Pathways to Building Block from Sugars Table 13-Pathways to Building Block

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9 2 2 5 Furan Dicarboxylic Acid Fdca 9 2 1 Pathways To Building Block From Sugars Table 13 Pathways To Building Block 1 (44.26 KiB) Viewed 65 times

9 2 2 5 Furan Dicarboxylic Acid Fdca 9 2 1 Pathways To Building Block From Sugars Table 13 Pathways To Building Block 2 (47.2 KiB) Viewed 65 times

9 2 2 5 Furan Dicarboxylic Acid Fdca 9 2 1 Pathways To Building Block From Sugars Table 13 Pathways To Building Block 3 (69.3 KiB) Viewed 65 times

9 2 2 5 Furan Dicarboxylic Acid Fdca 9 2 1 Pathways To Building Block From Sugars Table 13 Pathways To Building Block 4 (52.23 KiB) Viewed 65 times

9.2 2,5-Furan dicarboxylic acid (FDCA) 9.2.1 Pathways to Building Block from Sugars Table 13-Pathways to Building Block From Sugars [2,5-Furan dicarboxylic Acid (FDCA)] Type of pathway Technical Barriers Direct Uses of Building Block Chemical-Oxidative Dehydration dehydration of C6 sugars Selective dehydrations without side reactions Dehydration steps to anhydrides or lactones New heterogeneous catalyst systems (solid acid catalyst) to replace liquid catalysts Oxidations PET analogs with potentially new properties (bottles, films, containers) Alcohols (ROH) to acids (RCOOH) Avoiding exotic oxidants in favor of air, oxygen, dilute hydrogen peroxide Tolerance to inhibitory components of biomass processing streams Oxidation of aldehydes to acids and alcohols to aldehydes Unknown Biotransformation - Possibly enzymatic conversions 9.2.2 Primary Transformation Pathway(s) to Derivatives Table 14-Family 1: Reduction (Primary Transformation Pathway(s) to Derivatives: 2,5- Furan dicarboxylic Acid (FDCA)] Derivative or Technical barriers Potential use of derivatives Derivative Family Diols and Aminations Selective reduction of acids in presence of alkenes. Direct reduction of carboxylic acids to alcohols. New polyesters and nylons with new properties likely for fiber applications Knowledge of properties of polymer derivatives Levulinic and Succinic Acids Selective catalytic tools All uses of succinic and levulinic

Table 15- Family 2: Direct Polymerization [Primary Transformation Pathway(s) to Derivatives: 2,5-furan dicarboxylic Acid (FDCA)] Derivative or Technical barriers Potential use of derivatives Derivative Family Polyethylene terephthalate analogs. Reactivity of monomer. Controlling rates Furanoic polyesters for bottles, containers, films, Selective esterifications to control branching Control of molecular weight & properties Furanoic Polyamines Reactivity of monomer. Polyamide market for use in new nylons Controlling rates Selective esterifications to control branching Control of molecular weight & properties Building block: 2,5- Furan dicarboxylic acid (FDCA) Family 1- Reduction Family 2 - Direct Polymerization 9.2.3 Building Block Considerations Dehydration of the sugars available within the biorefinery can lead to a family of products. including dehydrosugars, furans, and levulinic acid. FDCA is a member of the furan family. and is formed by an oxidative dehydration of glucose. The process has been reported to proceed using oxygen, or electrochemistry. The conversion can also be carried out by oxidation of 5-hydroxymethylfurfural, which is an intermediate in the conversion of 6-carbon sugars into levulinic acid, another member of the top 10. Figure 7 describes some of the potential utility of FDCA. HO. OH HO₂C- Succinic acid CHLO, MW-118.09 2.5-Furandicarbaldehyde CHO, MW-124.00 2.5-Furandicarboxylic acid CHO, MW-126.11 HO OH 2.5-bis(aminomethyl)- tetrahydrofuran CHNO MW-130 19 2,5-dihydroxymethyl- tetrahydrofuran CHO, MW-132.16 Figure 7-Derivatives of FDCA "NH₂ HO 25-Dihydroxymethyl COM 128.13

9.2.4 Derivative Considerations FDCA has a large potential as a replacement for terephthalic acid, a widely used component in various polyesters, such as polyethylene terephthalate (PET) and polybutyleneterephthalate (PBT). PET has a market size approaching 4 billion lb/yr, and PBT is almost a billion lb/yr. The market value of PET polymers varies depending on the application, but is in the range of $1.00 3.00/b for uses as films and thermoplastic engineering polymers. The versatility of FDCA is also seen in the number of derivatives available via relatively simple chemical transformations. Selective reduction can lead to partially hydrogenated products, such as 2,5-dihydroxymethylfuran, and fully hydrogenated materials, such as 2,5-bis(hydroxymethyl)tetrahydrofuran. Both of these latter materials can serve as alcohol components in the production of new polyester, and their combination with FDCA would lead to a new family of completely biomass-derived products. Extension of these concepts to the production of new nylons, either through reaction of FDCA with diamines, or through the conversion of FDCA to 2,5-bis(aminomethyl)tetrahydrofuran could address a market of almost 9 billion lb/yr, with product values between $0.85 and 2.20/lb, depending on the application. FDCA can also serve as a starting material for the production of succinic acid, whose utility is detailed elsewhere in this report. The primary technical barriers to production and use of FDCA include development of effective and selective dehydration processes for sugars. The control of sugar dehydration could be a very powerful technology, leading to a wide range of additional, inexpensive building blocks, but it is not yet well understood. Currently, dehydration processes are generally nonselective, unless, immediately upon their formation, the unstable intermediate products can be transformed to more stable materials. Necessary R&D will include development of selective dehydration systems and catalysts. FDCA formation will require development of cost effective and industrially viable oxidation technology that can operate in concert with the necessary dehydration processes. A number of technical barriers also exist with regard to the use of FDCA (and related compounds) in the production of new polymers. Development and control of esterification reactions, and control of the reactivity of the FDCA monomer will be of great importance. Understanding the link between the discrete chemistry occurring during polymer formation, and how this chemistry is reflected in the properties of the resulting polymer will provide useful information for industrial partners seeking to convert this technology into marketplace products. 9.2.5 Overall Outlook The utility of FDCA as a PET/PBT analog offers an important opportunity to address a high volume, high value chemical market. To achieve this opportunity, R&D to develop selective oxidation and dehydration technology will need to be carried out. However, the return on investment might have applicability of interest to an important segment of the chemical industry.

Tasks Read the Executive Summary (p2-3) to familiarize yourself with the contents of the report. ● Read the information on 2,5-furan dicarboxylic acid (FDCA, section 9.2). Answer the questions below Questions 1. Describe the process of selection of the 12 biomass-based building blocks. 2. What pathway can lead to FDCA and from what type of sugar? Is it a chemical transformation or biotransformation? 3. What can be the potential direct use of FDCA? 4. What innovations in organic chemistry can address the technical challenges related to production of FDCA from biomass? 5. What derivatives or family of derivatives can be obtained from FDCA?