Functionalization of Long Chain Olefins and Fatty Acid Derivatives via Boron Intermediates
23 March 2018
UAntwerpen, Campus Hoboken, Aula Marcel Lanneer, Building B, ground floor - Salesianenlaan 90 - 2660 Hoboken
Prof Serge M.F. Tavernier, Prof ir. Kourosch Abbaspour Tehrani
PhD defence Lukasz Pazdur - Faculty of Applied Engineering
The chemical (related) industry is one of the largest industries in the world. At this moment this industry is mainly petrochemically based. Due to a rising shortage of petroleum and the stress between its function as fuel (source of energy) and its function as raw material (source of chemical building blocks), new strategies are deployed with respect to alternative raw materials that could lead to chemical building blocks.
Oleochemistry (centered on carbon containing molecules from natural oils and fats) seems an interesting way to obtain valuable chemical building blocks. A very interesting point is that it is a natural source of desirable long carbon-chain molecules, which can be further derivatized. The oleochemical approach has however also some disadvantages. A first important issue is the food versus fuel and/or food versus raw material discussion. The second issue is that there is a lack of long chain multifunctional, more specifically long chain α,ω-bifunctional molecules occurring in nature. Yet, such molecules can be used in high-value applications such as biopolymers and biolubricants.
As long chain bifunctional compounds, like α,ω-dicarboxylic acids are not provided by nature in sufficient amounts, it is important to develop a process to obtain these compounds in an environmentally friendly and economically viable way. It is important to design a process with an environmentally friendly catalyst and to optimize the process in such a way that not only edible clean fats/oils are used as starting material but also inedible fats/oils and maybe used oils/fats (used cooking oil).
This PhD work contributes to the valorization of unsaturated renewable materials into industrially relevant products. More specifically, the goal of this PhD work was to realize a sustainable method for the preparation of long carbon chain α,ω-bifunctionalized molecules starting from unsaturated long chain fatty acids and/or their derivatives. Two different methods to produce α – ω long chain building blocks were investigated: (1) the shift of mid-chain double bonds in derivatives of unsaturated (free) fatty acid esters by means of hydroboration-isomerization and (2) the synthesis and derivatization of long chain unsaturated dialkyl ethers.
The largest application of α,ω-bifunctional compounds (short as well as long type) can be situated in the production of biopolymers. Most of said biopolymers are based on polycondensation reactions (polyamides, polyesters, ...). Depending on the chain length of the α,ω-bifunctional compound the amount of polarity can be controlled in the biopolymer that has a polar repeating unit (e.g. ester group) that will be “diluted” with the long apolar hydrocarbon chain. At the moment a lot of apolar (petro)polymers are used that are not biodegradable (PE, PP, etc.). From literature it is found that most of all produced apolar (petro)polymers are not recovered and thus induce environmental pressure. In case long chain α,ω-bifunctional molecules with a high number of –CH2- groups in the chain could be produced, polymers could be made that could mimic the apolar (petro)polymers. This polyester type “Pseudo-PE” would be degradable and hence will give raise to less environmental pressure.