Single-site catalysts based on well-defined transition metal complexes have revolutionized polyolefin chemistry, providing both detailed mechanistic insight and precise control over polymer microstructure. Yet the most economical processes for olefin polymerization on scale continue to rely on solid catalysts. In this lecture I will describe a family of olefin polymerization catalysts prepared by cation exchange in metal-organic frameworks (MOFs). The resulting catalysts are single-site, providing polyolefins with low polydispersity. Furthermore, we exploit the modular structure of the MOF node as a handle for catalyst optimization, identifying catalysts for high comonomer incorporation and stereoselectivity. At the same time, low leaching and efficient morphological control provide evidence for robust immobilization of the catalytic species. Through spectroscopy and small molecule modeling, we demonstrate that cation exchange in MOFs provides a structurally predictable and mechanistically tractable platform for polymerization in the solid state.

Single-site heterogeneous catalysts for olefin upgrading enabled by cation exchange in metal-organic frameworks

254th National Meeting (2017)

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