Abstract

This article discusses physical and chemical properties, production methods, uses, and safe handling of the even-carbon-number linear -olefins. Other higher olefins (branched and/or internal) are discussed briefly. The principal classes of chemical reactions for olefins are addition reactions (electrophilic and free-radical) and substitution reactions. Common classes of transformations in industrial processes include oxo reaction (hydroformylation), oligomerization and polymerization, alkylation reaction, hydrobromination, sulfation and sulfonation, and oxidation. A low flash point is the main hazard associated with olefins. Flammability limits, autoignition temperatures, and flash points are listed. Olefins should be stored and shipped under an inert atmosphere as many applications are adversely impacted by low levels of moisture, peroxides, and oxygenates.

Most linear -olefins were produced from ethylene in 1993 with a total annual capacity of 2,136,000 metric tons. Ethylene oligomerization is discussed for the following commercial processes: (1) stoichiometric chain growth on aluminum alkyls followed by displacement (Albemarle); (2) catalytic chain growth on aluminum alkyls (Chevron-Gulf); (3) catalytic chain growth using a nickel-ligand catalyst (Shell); and (4) catalytic chain growth using a modified zirconium catalyst (Idemitsu).

Significant outlets for higher olefins are in the polymer, surfactant, and detergent industries. The C₄, C₆, and C₈ linear -olefins impart tear resistance and other desirable properties to linear low and high density polyethylene. The C₆, C₈, and C₁₀ linear -olefins give special properties to plasticizers used in flexible poly(vinyl chloride). The C₁₀ (and other carbon-number) linear -olefins provide premium value synthetic lubricants.