Polymers, Vol. 15, Pages 1360: Storage Stability of 6FDA-DMB Polyamic Acid Solution Detected by Gel Permeation Chromatography Coupled with Multiple Detectors

Polymers, Vol. 15, Pages 1360: Storage Stability of 6FDA-DMB Polyamic Acid Solution Detected by Gel Permeation Chromatography Coupled with Multiple Detectors

Polymers doi: 10.3390/polym15061360

Authors: Mei Hong Wei Liu Runxiang Gao Rui Li Yonggang Liu Xuemin Dai Yu Kang Xuepeng Qiu Yanxiong Pan Xiangling Ji

Polyamic acid (PAA) is the precursor of polyimide (PI), and its solution’s properties have a direct influence on the final performances of PI resins, films, or fibers. The viscosity loss of a PAA solution over time is notorious. A stability evaluation and revelation of the degradation mechanism of PAA in a solution based on variations of molecular parameters other than viscosity with storage time is necessary. In this study, a PAA solution was prepared through the polycondensation of 4,4′-(hexafluoroisopropene) diphthalic anhydride (6FDA) and 4,4′-diamino-2,2′-dimethylbiphenyl (DMB) in DMAc. The stability of a PAA solution stored at different temperatures (−18, −12, 4, and 25 °C) and different concentrations (12 wt% and 0.15 wt%) was systematically investigated by measuring the molecular parameters, including Mw, Mn, Mw/Mn, Rg, and [η], using gel permeation chromatography coupled with multiple detectors (GPC-RI-MALLS-VIS) in a mobile phase 0.02 M LiBr/0.20 M HAc/DMF. The stability of PAA in a concentrated solution decreased, as shown by the reduction ratio of Mw from 0%, 7.2%, and 34.7% to 83.8% and that of Mn from 0%, 4.7%, and 30.0% to 82.4% with an increase of temperature from −18, −12, and 4 to 25 °C, respectively, after storage for 139 days. The hydrolysis of PAA in a concentrated solution was accelerated at high temperatures. Notably, at 25 °C, the diluted solution was much less stable than the concentrated one and exhibited an almost linear degradation rate within 10 h. The Mw and Mn decreased rapidly by 52.8% and 48.7%, respectively, within 10 h. Such faster degradation was caused by a greater water ratio and less entanglement of chains in the diluted solution. The degradation of (6FDA-DMB) PAA in this study did not follow the chain length equilibration mechanism reported in literature, given that both Mw and Mn declined simultaneously during storage.