Abstract

We report the first observation of eliminative cationic polymerization within van der Waals (vdW) clusters following electron impact ionization at pressures of 10−8 Torr. The elimination reactions of C2H3Cl+ within the clusters terminate after three successive steps, each involving elimination of HCl or Cl. The results provide a mechanism for the early stages of gas phase cationic polymerization of vinyl chloride and demonstrate the feasibility of using vdW clusters as a means of studying gas phase cationic polymerization.

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