Isoprene is polymerized with a catalyst system consisting of a rhodium complex, allyl alcohol, and sodium dodecyl sulfate. The role of the emulsifiers was examined to elucidate the nature of the active species. Sodium dodecyl sulfate was found to be hydrolyzed even in a nonmicellar system to give sulfuric acid. Another experiment showed that isoprene was polymerized also by the catalyst system consisting of rhodium complex, allyl alcohol, and a strong acid such as toluenesulfonic acid, sulfuric acid, or nitric acid. From these results, it was assumed that an allyl ester of the strong acid was formed in the reaction system. The allyl ester presumably reacted with the rhodium complex to form a π-allyl complex, which was regarded as the active catalyst species in the isoprene polymerization. Allyl alcohol present in excess in the reaction system seemed to suppress cyclization reactions of the polymer formed.
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Matsui, E., Tsuruta, T. Mechanism of Polymerization of Isoprene Catalyzed by Rhodium Complex—Allyl Alcohol—Sulfonic Acid System. Polym J 10, 133–139 (1978). https://doi.org/10.1295/polymj.10.133
- Mechanism of Polymerization
- Sodium Dodecyl Sulfate
- Rhodium Catalyst
- Allyl Sulfonate
- Emulsion Polymerization
- Allyl Alcohol