Abstract
AbstractSummary: Equimolar mixtures of O‐permethylated and O‐perdeuteromethylated cyclodextrins were submitted to cationic ring‐opening polymerisation (CROP) with Et3OPF6 or BF3 · Et2O as initiator in dichloromethane. Reaction started after an incubation time and yielded a polymeric product, which was partially degraded again during competing chain transfer reaction. Average block length was determined by ESI‐MS after partial methanolysis and was found to be close to the theoretical value of 14 for β‐cyclodextrin in the early stage of the reaction, but decreased to 2–5 during further chain transfer reactions accompanied by an equilibration of α‐ and β‐configurated glucosidic linkages to a ratio of 64:36. Molecular weight was estimated from end group analysis and GPC to reach about 29 000 as a maximum. From 31P NMR spectra of the initiator it was obvious that PF is partly hydrolysed to PO2F under participation of the glass surface. magnified image
Published Version
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