Anionic polymerization of styrene (thermodynamics)

Abstract

Abstract The polymerization of styrene initiated by butyllithium in hydrocarbon solvents at elevated temperatures has been studied. Measurable amounts of monomer remained in equilibrium with the polymer in the temperature range covered (100–150°C.). The equilibrium concentrations were found to differ in the two solvents benzene and cyclohexane, but the calculated free energies of the polymer–monomer systems were the same after corrections had been applied for the different heats of solution. From the free energy data the heat and entropy of polymerization of styrene were calculated and found to agree with the calorimetric values.