SPONTANEOUS POLYMERIZATION OF STYRENE IN THE PRESENCE OF ACID - FURTHER CONFIRMATION OF THE MAYO MECHANISM

Flory and Mayo have proposed alternative mechanisms to explain the spontaneous polymerization of styrene. Both involve the formation of reactive styrene dimers capable of generating initiating radicals. However, the dimer intermediate proposed in the Mayo mechanism has defied all attempts at isolation. Since the Flory dimer would be expected to be stable to acid while the Mayo dimer would not, spontaneous styrene polymerization was studied in an acid environment to determine the effects on oligomer structure, polymerization rate, and polymer molecular weight. The results clearly show that the initiating Mayo dimer is deactivated by acid, forming high levels of inactive dimer. The decreased initiation results in a lower concentration of growing polymer chains, subsequently lowering the rate of termination (by chain coupling). The end result is a large shift of the spontaneous rate-molecular weight relation for polystyrene.