Microenvironment Modulation of Metal–Organic Frameworks (MOFs) for Coordination Olefin Oligomerization and (co)Polymerization

The majority of commercial polyolefins are produced by coordination polymerization using early or late transition metal catalysts. Molecular catalysts containing these transition metals (Ti, Zr, Cr, Ni, and Fe, etc.) are loaded on supports for controlled polymerization behavior and polymer morphology in slurry or gas phase processes. Within the last few years, metal–organic frameworks (MOFs), a class of unique porous crystalline materials constructed from metal ions/clusters and organic ligands, have been designed and utilized as excellent supports for heterogeneous polymerization catalysis whose high density and uniform distribution of active sites would benefit the modulations of molecular weight distributions of high‐performance olefin oligomers and (co)polymers. Impressive efforts have been made to modulate the microenvironment surrounding the active centers at the atomic level for improved activities of MOFs‐based catalysts and controlled selectivity of olefin insertion. This review aims to draw a comprehensive picture of MOFs for coordination olefin oligomerization and (co)polymerization in the past decades with respect to different transition metal active centers, various incorporation sites, and finally microenvironment modulation. In consideration of more efforts are needed to overcome challenges for further industrial and commercial application, a brief outlook is provided. Metal–organic frameworks (MOFs) are designed as excellent supports for heterogeneous polymerization catalysis, and impressive efforts are made to modulate the microenvironment for improving activities and selectivity of MOFs. This review aims to draw a comprehensive picture of MOFs for coordination olefin oligomerization and (co)polymerization with respect to different transition metal active centers, various incorporation sites, and finally microenvironment modulation.