The WCl6-e-Al-CH2Cl2 catalyzed polypentenamer formation via ring-opening metathesis polymerization (ROMP)

The synthesis of polypentenamer by an electrochemically generated metathesis polymerization catalyst from methylene chloride solution of WCl₆ was investigated. The active species formed by electroreduction of this salt under controlled potential of +900 mV at a platinum cathode with an aluminum anode were found to catalyze the ring-opening metathesis polymerization (ROMP) of cyclopentene, monocyclic olefin of relatively low strain, in high yield (89%) and at short period (32 min) under mild conditions. The effect of reaction parameters, e.g., olefin/catalyst ratio, reaction time, electrolysis time, catalyst aging, on the polymerization yield have been studied. The resulting polymer has been characterized by ¹H and ¹³C NMR, IR and gel permeation chromatography (GPC) techniques. Analysis of the polypentenamer microstructure by means of ¹³C NMR spectroscopy indicates that the polymer contains a mainly trans stereoconfiguration of the double bonds (σ_c = 0.31) and a slightly blocky distribution (r_tr_c > 1) of cis and trans double bond dyads (r_tr_c = 1.44). However, this electrochemical system is reluctant to facilitate the competing vinyl type addition polymerization reactions.