Abstract
The ring-opening polymerizations (ROPs) of lactones catalyzed by rare-earth metal trifluoromethanesulfonates (triflates) (RE(OTf) 3) were examined. Among various complexes, scandium triflate (Sc(OTf) 3) emerged as an effective catalyst in toluene. The ROP of lactones by Sc(OTf) 3 proceeded in a living fashion, and the number of polymer molecules was controlled by the amount of protic additives such as benzyl alcohol and H 2O. In other words, one molecule of Sc(OTf) 3 catalytically produced a number of polymer molecules (up to 40 molecules) depending on the amount of protic additives. The plausible mechanism was depicted as an activated monomer mechanism. The polylactones with a number-average molecular weight over 25,000 were successfully synthesized. Immobilization of RE(OTf) 3 was investigated in three ionic liquids, and cerium triflate (Ce(OTf) 4) showed relatively high catalytic activity in a biphasic system of 1-butyl-3-methylimidazolium hexafluoroantimonate and toluene in the ROP of ɛ-caprolactone (CL). The ionic liquid containing Ce(OTf) 4 was used, at least three times, in the ROP of CL without losing catalytic activity.
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