Structure–property relationships for film‐forming copoly(amide imide)s

Abstract

AbstractThin films of copoly(amide imide)s (coPAIs) from dichloro‐dianhydride of trimellitimide‐N‐acetic acid and mixtures of diphenylmethane diamine (DPA) and cardo 9,9′‐bis‐phenylfluorene diamine (CDA) cast from solutions in dimethylacetamide (DMAA) were characterized by wide‐angle and small‐angle X‐ray scattering (WAXS and SAXS), dynamic mechanical thermal analysis (DMTA) (temperature interval: 293–703 K, frequency range: 1–100 Hz), and thermogravimetric analysis (TGA) (nitrogen flux, temperature interval: 303–973 K). The mean interchain spacings (WAXS) smoothly increased with the CDA/DPA molar ratio from 0.55 nm for CDA/DPA = 0/1 up to 0.60 nm for CDA/DPA = 1/0. The smooth patterns of the SAXS curves for all coPAIs were explained by the smearing‐out of electron density differences between densely‐packed and loosely‐packed microregions of coPAIs due to the wide dispersion of their sizes. The step‐like patterns of the TGA traces in the temperature intervals below and above 600 K were associated with successive weight losses due to the evaporation of residual water and of DMAA, and to the thermal degradation of diamine and dianhydride chain fragments, respectively. As could be inferred from the TGA data, the loosely‐packed regions comprise about 25–35% of the total volume of studied coPAIs. The mechanical relaxations observed in all coPAIs at Tβ < Tα′ < Tα (DMA) were attributed to the onset of non‐cooperative segment motion in loosely‐packed regions, of cooperative segment motion in loosely‐packed regions, and of cooperative segment motion in densely‐packed regions, respectively. At constant frequency, the sub‐glass relaxations were roughly composition‐independent, while chain‐stiffening effect was assumed to be responsible for the smooth increase of Tα′ and Tα, as well as of the corresponding apparent activation energies with the CDA/DPA ratio. Copyright © 2003 John Wiley & Sons, Ltd.