Etude préliminaire de la stabilité à l'hydrolyse des polyimides 6F
Preliminary Study of the Hydrolysis Stability of 6f Polyimides
Institut Français du Pétrole
L'évaluation comparative du comportement en solution des polylmides 6F fait ressortir que ces nouveaux polymères, doués d'une stabilité thermique élevée par référence à l'analyse thermogravimétrique, ont, par contraste, une résistance beaucoup plus limitée aux influences ioniques et que l'hydrolyse, qui entraîne une réduction substantielle de leur masse moléculaire, est, dans leur cas, un processus de dégradation d'importance majeure.
Despite its importance, particularly during the phase-inversion creation of asymmetrical gaseous-permeation membranes, the behavior in solution of polyImides derived from 4,4'-hexafluoroisopropylidenediphthalic anhydride has not, to our knowledge, been the subject of any published report. The present project was thus undertaken to assess the hydrolysis resistance of such polymers. This article describes and interprets some results highlighting the influence of structural factors. The products, which differ in the nature of both the initial diamine and dianhydride, were prepared by thermal polyheterocyclization in a single stage in different solvents at 200°C, and their stability was determined by the variations in their intrinsic viscosity after aging in a sealed tube at 90°C. Hydrolysis does not affect all 6F polyImides in a uniform way but seems to be governed by differences in the chemical affinity and in the morphology of the chains. Polymers having an increasing number of alkyl groups on the aminated remainder show a less and less marked susceptibility. A more specific fragility, however, affects polyImides having a carboxylic acid group. Other polar substituents have a stabilizing influence. A comparison with other polyImides is undeniably unfavorable to 6F derivatives. Degradation is very marked in dipolar aprotic solvents, whereas it appears quite limited in m-cresol. It apparantly cannot be blamed on the possible presence of uncyclized acid-amide units. The influence of the amount of water and of the temperature suggests rather a balanced opening cycle of the imide ring. The fundamental study that was undertaken on monomer models by means of the NMR of fluorine will doubtless be able to determine the mechanism involved, but this handicap of 6F polyImides should not rule out the outlook for their industrial use as separation membranes.
© IFP, 1993