THERMOLYTIC BEHAVIOR OF POLYBUTADIENYLLITHIUM AND POLYSTYRYLLITHIUM IN ETHYLBENZENE AT HIGH-CONCENTRATIONS

The polymerization of butadiene and styrene with lithium and lithium a lkyls has been extensively studied. The kinetics and mechanism of the pyrolysis of alkyllithium compounds has also been investigated thoroug hly. The mechanism of these elimination reactions is conveniently eluc idated by manometric methods, and mechanistic interpretations have bee n proposed. However, there are less published accounts of the thermal stability of polymer-lithium systems. There is a need to have kinetic data describing the thermal termination of ''living'' polymers at lith ium concentrations approaching those of commercial polymerization syst ems. This paper will discuss the thermal stabilities of concentrated s olutions in ethylbenzene of polystyryllithium and polybutadienyllithiu m.