The research project is aimed towards the development of new heterogeneous catalysts for oligo- and polymerizations of olefins and other monomers. The main idea is to combine the high activity and selectivity of homogeneous single site catalysts with the exceptional size-exclusion effect of metal-organic frameworks. The precise adjustment of pore structure in 3D MOFs is expected to become a perfect tool to control the surrounding of the active centers during the oligo-/poly-merization, and thus, to control the chemo-, regio- and stereo-selectivity of the processes, predetermining the microstructure of the products.
One of the main challenges of the project is the design of MOF architectures incorporating the accessible catalytic centers with a defined chemical structure. Several parameters such as composition and geometry of building blocks, chemical reactivity of components, conditions of synthesis, etc. should be compliant to achieve the reproducible formation of MOFs with the desired properties. A number of synthetic strategies including the so called “pillaring approach” will be tested in this respect.
Polymerization experiments with thus prepared MOF-based molecular-defined heterogeneous catalysts (MDHC) and the consequent analysis of distributions of products parameters such as molecular weight, branching, regio- and stereo-regularity should reveal the efficiency of the proposed approach and, perhaps, validate it for potential research or industrial applications. For example, it is expected to influence the Schulz-Flory distribution of the oligo- and polymer products in higher -olefin formation processes from ethylene by control of the MOF-channel size. Consecutive studies will transfer the idea of MDHCs to further improve regio-, stereo- and enantio-selectivity of other catalytic organometallic transformations.
Hindelang, K., et al.: "Tandem Post-Synthetic Modification for Functionalized Metal-Organic Framework via Epoxidation and Subsequent Epoxide Ring-Opening", 2012.
Hindelang, K., et al.: "Functionalization of Metal–Organic Frameworks through the Postsynthetic Transformation of Olefin Side Groups", 2013.