Polyimides containing oxyethylene units. Part 4: Polymerization of dianhydrides containing ether linkages

摘要

The development of new composite resins for various aerospace applications is attempted. Although it is highly desirable that these polymers be soluble in order to facilitate processing, they must display considerable solvent-resistance in use. A recent approach has involved the synthesis of a new series of polyimides containing flexible linkages. The polymers were prepared by the polymerization of aromatic dianhydrides with diamines containing oxyethylene linkages. For example, the polymerization of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) with 1,2-bis(4-aminophenoxy)ethane (1a) and bis2-(4-aminophenoxy)ethylether (lb), afforded highly crystalline polyimides that were completely insoluble. However, a polyimide that was amorphous and soluble was obtained from the polymerization of BTDA and an isomer of lb, i.e., bis2-(3-aminophenoxy)ethyl ether (4b). In an attempt to obtain a soluble, amorphous polyimide that could be annealed into a crysalline state, block copolymers of 1b and 4b and BTDA were prepared. Copolymers containing less than 20 weight 1b were soluble in organic solvents. However, these polymers did not crystallize when heated above their Tg's. Copolymers containing higher levels of 1b were semicrystalline and insoluble. The polymerization of the diamines containing oxyethylene linkages with 4,4'-oxydiphthalic anhydride (ODPA) and a new dianhydride, i.e., 4,4'-oxyethyleneoxyethyleneoxydiphthalic anhydride (OEDA) was investigated. It was postulated that the use of these more flexible dianhydrides would result in more processable polyimides.