Thermal stability of “living” polymer–lithium systems

Abstract
The thermal stabilities of polybutadienyllithium, polyisoprenyllithium, and polystyryllithium solutions have been determined in hydrocarbon solvents. Kinetic analysis indicated that a complex mechanism was involved in the thermolysis of polybutadienyllithium. The thermal stability was observed to increase with increasing lithium concentration, suggesting the presence of competitive reactions in addition to the expected elimination of lithium hydride. The thermal stability of the three systems studied was consistent with their reported degrees of association: dimeric polystyryllithium was less stable than tetrameric polyisoprenyllithium or hexameric polybutadienyllithium.

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