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Due to reasons of sustainability and conservation of resources, polyurethane (PU)-based systems with preferably neutral carbon footprints are in increased focus of research and development. The proper design and development of bio-based polyols are of particular interest since such polyols may have special property profiles that allow the novel products to enter new applications. Sophorolipids (SL) represent a bio-based toolbox for polyol building blocks to yield diverse chemical products. For a reasonable evaluation of the potential for PU chemistry, however, further investigations in terms of synthesis, derivatization, reproducibility, and reactivity towards isocyanates are required. It was demonstrated that SL can act as crosslinker or as plasticizer in PU systems depending on employed stoichiometry. (ω-1)-hydroxyl fatty acids can be derived from SL and converted successively to polyester polyols and PU. Additionally, (ω-1)-hydroxyl fatty acid azides can be prepared indirectly from SL and converted to A/B type PU by Curtius rearrangement.
The synthesis of 17-hydroxy-oleic acid based oligomeric esters was investigated with immobilized Pseudozyma antarctica Lipase B and hexanediol as co-substrate. The effects of different reaction parameters on velocity and product composition at equilibrium conditions were analyzed. The synthesis of oleic acid esters was used as a reference system for initial evaluation of reaction parameters. The reaction with oleic acid and hexanediol was fastest at an enzyme concentration of 5% at 60 °C and high conversions of > 90 % were achieved in non-polar solvents in the presence of molecular sieves. In heptane an oleic acid conversion of 96 % was reached with a final diester to monoester ratio of > 4:1. In syntheses trials with 17-hydroxy-oleic acid the formation of oligomers was verified with GPC, however; conversion was generally lower than with oleic acid. Removal of hydroxyl fatty acid monomers and dimers and the formation ester functionalities could be verified by GC analysis. An increase of the degree of oligomerization was observed simultaneously by GPC analysis. The number-average molecular weight was around 1400 in the best trials corresponding to a degree of oligomerization of around 4 units of hydroxyl-fatty acid attached to a hexanediol core. Though transformations were not complete, the final oligomer size was in the lower range of polyester diols used for polyurethane manufacturing.
Due to the worldwide shortage of petrochemical based resources, the usage of renewable bio-based raw materials for established and novel products becomes increasingly important.[1] Such bio-based resources are already used for the fabrication of a variety of products, e. g. paper, lubricants, detergents or cosmetics. In the future they are expected to emerge in many more applications in industry and household.[1]
A very promising approach relies on the use of glycolipids as a source of hydroxy-oleic acid.[2] Microbial glycolipids are produced for instance via fermentation from natural resources such as plant oils and sugar.[3] After fermentation complex product mixtures are obtained with the composition depending on the microorganism, substrate and fermentation time.[3] The successful use of microbial glycolipids and hydroxy-oleic acid (HOA) derived therefrom as bio-based intermediates requires reliable analytical methods as well as robust manufacturing processes for the synthesis and cleavage of bio-based molecules. In order to obtain hydroxy-oleic acids as bio-based intermediates, the acidic cleavage of microbial derived sophorolipid was investigated. In addition the implementation of HOA in polyurethane (PU) systems was explored.