This study reported a method to prepare fully aromatic macrocycle-terminated polyimides (MC-PI). The macrocycle of aryl ether ketones was prepared from (4-amino)phenylhydroquinone and a di-fluoro monomer under pseudo high dilution condition. Novel aromatic fully MC-PI oligomers were successfully prepared by the reaction of 2,3,3′,4′-biphenyltetracarboxylic diandhydride with 2,5-bis(4′-aminophenoxy)-biphenyl and sulfur-containing macrocycle of aryl ether ketone. The MC-PI oligomers were cross-linkable in the heating, and the glass transition temperatures of the polyimides increased after thermally cured. The cross-linking reaction of MC-PI could form fully aromatic thermosetting polyimide by ring-opening reaction. After cross-linking, these polyimides showed higher glass transition temperatures and excellent thermal stability. Copyright © 2013 John Wiley & Sons, Ltd.
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