Synthesis and properties of copolypyromellitimides

Abstract

AbstractCopolyamic acids with different proportions of diamine component were prepared by polymerizing different molar ratios of diamines—benzidine (B)/4,4′‐diaminodiphenyl ether (E) and p‐phenylene diamine (P)/4,4′‐diaminodiphenyl methane (M)—with pyromellitic dianhydride (PMDA) in dimethylacetamide (DMAc) at room temperature. Diamine component can be arranged in regular sequence through various reaction processes, such as alternating, block, and partial block copolymers. In addition, it can also be arranged in random sequence to obtain random copolymers. Thermal cyclodehydration of polyamic acids results in the corresponding polyimides. Polymers are characterized by viscosity, thermal stability, crystallinity, and mechanical strength. It was found that an increase in the proportion of more flexible diamine component (such as E and M) incorporated in polymer chain results in copolyimides with better mechanical strength and causes a fall in viscosity of copolyamic acids and a decrease in thermal stability and crystallinity of copolyimides. Within the copolymers of the same composition, the thermal stability, crystallinity, and mechanical strength of ordered polymers are superior to those of random polymers. The results of viscosity measurements imply that the anhydride‐terminated prepolymer is easily destroyed by water in the solution, so that the ultimate viscosities of alternating and block copolyamic acids are inferior to those of random ones, but this phenomenon can be improved through the preparation of the partial block copolymers.