| Abstract: | Copolymerizations of a six‐membered ring spiro‐orthocarbonate bearing adamantane backbones ( AD ‐ SOC , 1 ) and a monofunctional epoxide, PGE , in the presence of cationic initiators such as Sc(OTf)3 were carried out under various reaction conditions. As a result, instead of the anticipated poly(ether‐ether‐carbonate) 11 , two types of copolyethers ( 12 and 18 ) consisting of two or three types of ether components having different substituent groups were unusually formed along with the evolution of carbon dioxide gas, in which AD ‐ SOC efficiently acted as the corresponding oxetane equivalent monomers 3 and 4 . Furthermore, the copolymerization behavior, including the formation of copolyethers 12 and 18 , unexpectedly and significantly depended on the reaction conditions, such as the concentration of the initiator. For example, the copolymerizations with 5 mol % of Sc(OTf)3 mainly afforded copolyether 18 , while those with 1 mol % mainly gave copolyether 12 . In addition, treatments with 5 mol % of Sc(OTf)3 also yielded CH2Cl2, THF, and DMF‐insoluble networked products, indicating relatively higher thermal stability compared with a common polyether. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1729–1740, 2005 |
