A comparison of poly(ether imide)s from diamines with 2-aminophenoxy or 4-aminophenoxy units: Synthesis, characterization and properties

A series of new 3- and 4-ring bis(2-aminophenoxy) aromatic diamines were prepared. These, and corresponding, conventional bis(4-aminophenoxy) diamines were reacted with several aromatic bis(ether anhydride)s to form poly(ether imide)s. The diamines with 4-aminophenoxy groups gave high-molecular-weight polymers that were cast into films with good mechanical properties. In contrast, in almost all cases, diamines with 2-aminophenoxy groups only gave low-molecular-weight powdery products that could not be cast into coherent films. The low-molecular-weight products, prepared from stoichiometrically equal amounts of monomers, were examined by mass spectrometry and shown, in most cases, to consist primarily of cyclic oligomers; traces of linear oligomers were identified in some samples. Apart from a polyimide prepared from pyromellitic dianhydride and 4,4'-bis(2"-aminophenoxy)biphenyl, the only products found to contain significant proportions of linear oligomers were those prepared with a stoichiometric imbalance of monomers. End groups of the various linear oligomers were identified. The 2-aminophenoxy groups predispose the oligomers to cyclize as amic acids, and to remain as cyclics on imidization. In some cases [1 + 1] cyclic oligomers were observed although the most common species were the [2 + 2] cyclic dimers. (c) 2006 Elsevier Ltd. All rights reserved.