cis,cis-Muconic acid isomerization and catalytic conversion to biobased cyclic-C6-1,4-diacid monomers
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The function of the Department of Chemical and Biological Engineering has been to prepare students for the study and application of chemistry in industry. This focus has included preparation for employment in various industries as well as the development, design, and operation of equipment and processes within industry.Through the CBE Department, Iowa State University is nationally recognized for its initiatives in bioinformatics, biomaterials, bioproducts, metabolic/tissue engineering, multiphase computational fluid dynamics, advanced polymeric materials and nanostructured materials.
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The Department of Chemical Engineering was founded in 1913 under the Department of Physics and Illuminating Engineering. From 1915 to 1931 it was jointly administered by the Divisions of Industrial Science and Engineering, and from 1931 onward it has been under the Division/College of Engineering. In 1928 it merged with Mining Engineering, and from 1973–1979 it merged with Nuclear Engineering. It became Chemical and Biological Engineering in 2005.
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1913 - present
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- Department of Chemical Engineering (1913–1928)
- Department of Chemical and Mining Engineering (1928–1957)
- Department of Chemical Engineering (1957–1973, 1979–2005)
- Department of Chemical and Biological Engineering (2005–present)
- College of Engineering(parent college)
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Abstract
Renewable terephthalic and 1,4-cyclohexanedicarboxylic acids can be produced from biomass via muconic acid using a combination of biological and chemical processes. In this conversion scheme, cis,cis-mucononic acid is first obtained by fermentation using either sugar or lignin monomers as a feedstock. The diunsaturated cis,cis-diacid is then isomerized to trans,trans-muconic acid, reacted with biobased ethylene through Diels–Alder cycloaddition, and further hydrogenated or dehydrogenated to yield the desired 100% renewable cyclic dicarboxylic acid. The isomerization of cis,cis- to trans,trans-muconic acid represents the main bottleneck in this process due to undesired side reactions that promote ring closing to form lactones. Therefore, new technologies for the selective isomerization of muconic acid are urgently needed. Here, we studied the corresponding reaction kinetics to elucidate the mechanisms involved in both the isomerization and cyclization reactions with the objective to identify conditions that favor the selective formation of trans,trans-muconic acid. We demonstrate that the reactivity of muconic acid in aqueous media strongly depends on pH. Under alkaline conditions, cis,cis-muconic acid is deprotonated to the corresponding muconate dianion. This species is stable for extended periods of time and does not isomerize. Conversely, cis,cis-muconic acid readily isomerizes to its cis,trans-isomer under acidic conditions. Prolonged heating further triggers the intramolecular cyclizations through reaction of the carboxylic acid and alkene functionalities. The formation of the muconolactone and its dilactone is kinetically favored over the isomerization to trans,trans-muconic acid over a broad range of conditions. However, strategies involving the chelation of the carboxylates with inorganic salts or their solvation using polar aprotic solvents were found to hamper the ring closing reactions and allow the isomerization to trans,trans-muconic acid to proceed with high selectivity (88%). The obtained compound was further reacted with ethylene and hydrogenated to 1,4-cyclohexanedicarboxylic acid, an important monomer for the polyester and polyamide industries.
Comments
This is a manuscript of an article published as Carraher, Jack M., Toni Pfennig, Radhika G. Rao, Brent H. Shanks, and Jean-Philippe Tessonnier. "cis, cis-Muconic acid isomerization and catalytic conversion to biobased cyclic-C 6-1, 4-diacid monomers." Green Chemistry 19, no. 13 (2017): 3042-3050. DOI: 10.1039/C7GC00658F . Posted with permission.