Postintercalative Polymerization of Aniline and Its Derivatives in Layered Metal Phosphates

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Abstract

The formation of polyaniline in the layered metal phosphates, α-Ti(HOPO3)2•H2O, α-Zr(HOPO3)2•H2O, and HUO2PO4•4H2O is reported. Aniline and A-phenyl-1,4-phenylenediamine (PPDA) are intercalated in the layered phosphates to form the precursors for polymerization. X-ray diffraction patterns show interlayer expansions with titanium phosphate and zirconium phosphate, consistent with a bilayer of these molecules in the gallery. In contrast, only a monolayer is intercalated in uranyl phosphate. After thermal treatment at 130 °C in air, the intercalated aniline and PPDA are slowly polymerized by ambient oxygen. The formation of polyaniline was confirmed by FT-IR, UV/vis and EPR spectroscopies as well as magnetic susceptibility measurements. Following polymerization, the interlayer spacing slightly increases from 10.46 to 11.8 Å for anilinium/uranyl phosphate but dramatically decreases from 28.3 to 20.5 Å for PPDA/Zr(HOPO3)2 and from 18.87 to 13.25 Å for anilinium/Ti(HOPO3)2, suggesting a monolayer of polyaniline inside the uranyl phosphate and titanium phosphate structures but a bilayer in Zr(HOPO3)2. Gel permeation chromatography was used to determine the MW of the intercalated polyaniline. Prolonged heating in air results in cross-linked polymer in the galleries. All compounds are insulators.

Original languageEnglish
Pages (from-to)1525-1533
Number of pages9
JournalChemistry of Materials
Volume7
Issue number8
DOIs
Publication statusPublished - Aug 1995

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ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

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