Polymerization and Selective Oligomerization of Alkenes

Polymerizations of alkenes, with or without functional groups, are very important industrial processes. This chapter discusses the role of catalysts in the manufacture of three widely used polymers. These polymers are polyethylene (PE), polypropylene (PP), and polybutadiene (PB). It examines the nature of the catalyst and the general mechanism of the polymerization reaction. The traditional recipes for Ziegler–Natta catalysts have been substantially modified to give catalysts, which are orders of magnitude more active than the original ones. The chapter focuses on some of the essential structural and mechanistic features of metallocenes and nonmetallocene single‐site catalysts and that of the cocatalyst. It addresses the role of methyl aluminoxanes (MAO) as a cocatalyst. The chapter describes the relationships between the structures of single‐site precatalysts and the microstructures of the resultant polymers. It reviews the first step of SHOP, i.e., the oligomerization of ethylene to give linear a‐olefins by soluble nickel catalysts.