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978-3-8439-0605-0, Reihe Technische Chemie
Andreas J. Vorholt
Biomonomere aus Carbonylierungen von Fettstoffen
213 Seiten, Dissertation Technische Universität Dortmund (2012), Hardcover, A5
Fats and oils are easily available renewable resources. Functionalised fats are used for production of materials e.g. surfactants. The chemical conversion of unsaturated fatty acid esters with carbon monoxide plays an important role in functionalisation of fatty compounds.
The purpose of this dissertation was to establish various carbonylation reactions with fatty acid methyl esters. The focus was on high product yields by application of commercially available, homogeneous catalysts with the renewable resource oleic acid methyl ester. The investigations led to parameters making the processes feasible for technical application.
The hydroaminomethylation of diethylamine, proline and 3-methylaminopropionitrile and hydroesterification of oleic acid methyl esters were optimized and transferred to thermomorphic solvent systems in order to achieve convenient catalyst recycling. This afforded very low metal leaching values in the product phases during all four reactions. Furthermore, it was possible to recycle the catalyst phases in several runs which were accomplished by ongoing catalyst activity. Based on the experimental data two proposals for a technical implementation have been developed. One process covers hydroaminomethylation of 3-methylaminopropionitrile and consecutive hydrogenation of the nitrile, the second comprise hydroesterification of oleic acid methyl ester.
It is also presented the first tandem hydroformylation and -alkylation leading to high yields and high ee values. As another promising carbonylation the hydroamidation of unsaturated fatty acid esters has been examined.
Starting from easily available unsaturated fatty acid esters, it was possible to synthesise bifunctional molecules with high turnover values by functionalization with alkyl amines, amino acids, aminonitrils, alcohols and primary amines. Diesters, diamides, amino esters and alcohol esters were synthesized with yields up to 90 %. These products can be used as surfactants or as biomonomers.