Effective Conversion of Amide to Carboxylic Acid on Polymers of Intrinsic Microporosity (PIM-1) with Nitrous Acid

Abstract

Carboxylate-functionalised polymers of intrinsic microporosity (C-PIMs) are highly desirable materials for membrane separation applications. The recently reported method to afford C-PIMs was via an extensive base hydrolysis process requiring 360 h. Herein, a novel and effective method to convert PIM-CONH₂ to C-PIM using nitrous acid was studied. The chemical structure of C-PIM was characterised by ¹H NMR, ¹³C NMR, FTIR, elemental analysis, UV-Vis, TGA and TGA-MS. Complete conversion from amide to carboxylic acid groups was confirmed. Decarboxylation of C-PIM was also successfully studied by TGA-MS for the first time, with a loss of <i>m</i>/<i>z</i> 44 amu (CO₂) observed at the first degradation stage. TGA also revealed decreased thermal stability of C-PIM relative to PIM-CONH₂ under both N₂ and air atmosphere_. Gel permeation chromatography (GPC) analysis showed continuous molecular weight degradation of C-PIM with extended reaction time. Aromatic nitration was also observed as a side reaction in some cases.