Stereospecific polymerization of olefins with supported Ziegler − Natta catalysts

The discovery of Ziegler − Natta catalysts has been one of the greatest developments in technology for the synthesis of stereoregular polymers in both academy and industry since the 1950s. In particular, the development of the fourth generation Ziegler − Natta catalyst with MgCl 2 as support brings a revolutionary improvement to the properties of manufactured polyolefins and stimulates people to explore the stereospecific polymerization of α‐olefin and diene monomers, which supplies the power to synthesize a new type of polyolefin materials. Although research on single‐site catalysts has attracted a lot of attention in recent years, the ‘old’ and conventional Ziegler − Natta catalysts are still being developed vigorously due to their unique industrial advantages such as low cost, high catalytic efficiency and high stereospecificity. In this mini‐review, we mainly summarize the development of the conventional supported Ziegler − Natta catalyst system and the stereoregular polyolefins synthesized with supported Ziegler − Natta catalysts.