Perfectly alternating segmented polyimide-polydimethyl siloxane copolymers via transimidization

New strategies for the synthesis of perfectly alternating segmented polyimide-polydimethyl siloxane copolymers were developed by utilizing a transimidization method. Imide oligomers endcapped with 2-aminopyrimidine were reacted with aminopropyl terminated (dimethyl siloxane) oligomers to afford perfectly alternating segmented imide siloxane copolymers. The polymerization was conducted in solvents such as chlorobenzene and chlorofrom. High molecular weight, fully imidized perfectly alternating segmented imide siloxane copolymers were obtained within 2 h at temperatures of 60-110°C. The mechanism of the reaction was further elucidated via model compounds and NMR characterization. The block copolymers exhibited two T_gs due to the microphase separation of the polyimide and polysiloxane phases. The T_g of the polyimide phase was a function of the length of the polyimide block. However, partial phase mixing was also evident from the DSC results on the imide siloxane copolymers prepared with low molecular weight polyimide segments. Thermooxidative stability and tensile properties of the perfectly alternating segmented imide siloxane copolymers were found to be principally dependent on the amount of poly (dimethyl siloxane) incorporated in the copolymer and did not correlate with the poly (dimethyl siloxane) or polyimide block lengths. The stress-strain behavior of both solvent cast films or molded films is also reported. © 1994 John Wiley & Sons, Inc.