Pendent Polyimides using Mellitic Acid Dianhydride. I. An Atomic Oxygen-resistant,Pendent 4,4′-ODA/PMDA/MADA Co-polyimide Containing Zirconium

Abstract

The goal of this research is to increase the metal-organic concentration in Kapton-like polyimides (PIs) to achieve increased atomic oxygen (AO) resistance while retaining desirable film properties. Co-polyamic acid (PAA) precursors were prepared using a novel polymer building block, mellitic acid dianhydride (MADA), to provide sites for pendent group attachment. Attachment of an amino group-functionalized zirconium complex to the co-PAA precursors was facilitated by a stoichiometric amount of dicyclohexylcarbodiimide. The viscous solutions which resulted were characterized by thin layer chromatography (TLC), viscosity, and gel permeation chromatography (GPC), or treated with excess poor solvent to precipitate powder samples, or cast onto glass slides and heated to produce imidized films. Powder samples were dissolved in deuterated solvent for proton nuclear magnetic resonance analysis, or characterized by thermogravimetric analysis and differential scanning calorimetry. Film samples were characterized by Fourier transform infrared and by scanning electron microscopy (SEM) before and after exposure to atomic oxygen in a plasma asher. The spectroscopic data are consistent with the expected amic acid and imide, pendent and non-pendent structures. TLC, viscosity and GPC results confirm the polymeric nature of the pendent and non-pendent co-PAA precursors, with inherent viscosities (<₀)of 0.76 and 0.65 and weight average molecular weights (M_w) estimated to be 61 000 and 138 000 Dalton, respectively. As expected, visual and SEM inspections of pendent and non-pendent co-PI films reveal extensive surface roughening upon exposure to AO, with the former developing a white surface layer known from model compound studies to be predominantly zirconium dioxide. Additional reports describing the effects of polymer structure and pendent group concentration on film properties and AO resistance are in preparation.

Keywords

mellitic acid dianhydride benzenehexacarboxylic acid dianhydride polyimide pendent atomic oxygen zirconium

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