Industrial research in acrylates synthesis

27 sept 2012
16:20 – 16:50

Industrial research in acrylates synthesis

 

co22For more than three decades the catalytic synthesis of acrylates from the cheap and abundantly available C1 building block CO2 and alkenes has been an unsolved problem in catalysis research, both in academia and industry. Acrylates and their downstream products are ubiquitous in daily life as hygiene products, coatings, adhesives or plastics etc. and they are manufactured globally on a multi million ton level. Thus, a CO2-based route to such world-scale chemicals is economically most attractive, but, due to thermodynamic and kinetic hurdles, also highly challenging. Since the revolutionary work of Hoberg,[1] nickelalactones (1) are discussed as possible intermediates in a hypothetic catalytic cycle but i) an oxidative coupling of CO2 and ethylene has so far only been observed for selected ligands at low temperature (A), ii) despite first attempts,[2,3] the productive -H elimination (B) is unknown as are, iii) Nickel acrylate complexes (C), and iv) the final ligand exchange of p-complexes to ethylene to re-initiate the cycle (D).

The first homogeneous catalyst system ever based on a Ni-complex is presented. It permits the clearly catalytic synthesis of Na-acrylate from CO2, ethylene and a base, as demonstrated by a TON > 10 at this stage.[4]

 

[1]    H. Hoberg, Y. Peres, C. Krüger, Y. H. Tsay, Angew. Chem. Int. Ed. 1987, 26, 771-773.

[2]    R. Fischer, J. Langer, A. Malassa, D. Walther, H. Görls, G. Vaughan, Chem Commun. 2006, 2510-2512.

[3]    C. Bruckmeier, M. W. Lehenmeier, R. Reichardt, S. Vagin, B. Rieger, Organometallics 2010, 29, 2199-2202; S. Y. T. Lee, M. Cokoja, M. Drees, Y. Li, J. Mink, W. A. Herrmann, F. E. Kühn, ChemSusChem 2011, 4, 1275-1279.

[4]    M. L. Lejkowski, R. Lindner, T. Kageyama, G. É. Bódizs, P. N. Plessow, I. B. Müller, A. Schäfer, F. Rominger, P. Hofmann, C. Futter, S. A. Schunk, M. Limbach, Chem. Eur. J. 2012, DOI: 10.1002/chem.201201757.