Cationic Polymerization Using Heteropolyacid Salt Catalysts

Abstract

Acid catalysts are used in the production of several commercially important lubricant additives, including dispersants and antioxidants. While the use of conventional mineral and Lewis acids still dominate existing production, heterogeneous solid acid catalysts provide a future option for cost reduction and pollution prevention. The heteropolyacids discussed in this presentation are based on the parent phosphotungstic acid, H₃PW₁₂O₄₀, which has been studied for many years as solid acid catalysts especially by Japanese researchers. A particular class of heterpolyacid salts of the formula (M⁺)_2.5H_0.5PW₁₂O₄₀ exhibit enhanced catalytic activity, which is believed to be due to the formation of a phase with nano-sized crystallites, as has been reported by Misono and coworkers. This class of heteropolyacid salts has been successfully applied by Lubrizol researchers to the production of high-reactivity polyisobutylene, a polymer used in the production of dispersants for commercial lubricants. Most notably, the catalyst of the formula (NH₄ ⁺)_2.5H_0.5PW₁₂O₄₀ provides high conversion to the desired reactive vinylidene isomer and a unique polymer molecular weight distribution, which results in improved performance characteristics when compared to existing commercial AlCl₃ and BF₃ catalysts. Catalyst performance is effectively optimized by catalyst concentration in a slurry reactor, catalyst calcination temperature and loading on a silica support. This class of catalysts has also been successfully applied to a number of other acid-catalyzed processes for the production of additives, including for the antioxidant nonyl diphenylamine.