Mechanism of ring-opening and elimination cooligomerization of cyclic carbonates and ε-caprolactone: Formation of cyclic cooligomers

The cooligomerization reactions of the comonomers ethylene carbonate-propylene carbonate, ethylene carbonate-ε-caprolactone and propylene carbonate-ε-caprolactone initiated by the p-tert-butylphenol/KHCO3 system were investigated by means of electrospray ionization mass spectrometry combined with liquid chromatography. Three major cooligomer series were found in each case which were identified such as cooligomers with tert-butylphenol and hydroxyl headgroups. The presence of cyclic cooligomers was also unambigously observed. In addition, cooligomers carrying carbonate linkages were also identified, however, their fraction was very small compared to the cooligomer series without carbonate linkages. Besides the cooligomerization reaction, homooligomerization of ethylene and propylene carbonate was observed, as well as no linear homooligomers of ε-caprolactone were detected. Based on the LC-ESI MS results a mechanism is proposed for the formation of cyclic co-oligomers and the chain degradation of cooligomers containing carbonate linkages.