Molecular Weight Dependence of Associative Behavior in Polyimide/DMF Solutions

Eight 6FDA-TFDB polyimide (PI) samples with absolute molecular weights ranging from 1.25 × 105 g·mol−1 to 3.11 × 105 g·mol−1 are obtained by precipitation fractionation. Rheological experiments are conducted to determine the influence of molecular weight on the associating behavior of PI in N,N′-dimethylformamide (DMF) solutions in a broad volume fraction, including abnormal steady shear flow, solution heterogeneity, and scaling behavior. Abnormal flow behaviors, i.e., multi-region shear thinning and weak shear thickening, are studied, and these behaviors have not been reported in literature. The heterogeneity of PI/DMF solutions is examined by dynamic rheological test. By plotting ηsp versus φ/φη, four concentration regions of I–IV can be distinguished for all PI samples with various molecular weights. The scaling results in different concentration regions are in good agreement with the associative polymer theory proposed by Rubinstein and Semenov. The scaling exponents do not show molecular weight dependence in concentration regions I and II. In concentration regions III and IV, the scaling exponents change little when the molecular weight is below 242 k but increase when the molecular weight increases from 242 k to 311 k. This work can help us to understand polyimide solution properties from dilute to semidilute entangled solutions, and will guide the polyimide solution preparation for different processing.