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 N-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
Publication statusPublished - 1995

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Aniline
Phosphates
Metals
Polymerization
Derivatives
Polyaniline
Monolayers
Gel permeation chromatography
Air
Magnetic susceptibility
Diffraction patterns
Paramagnetic resonance
Polymers
Titanium
Heat treatment
Spectroscopy
Oxygen
Heating
X ray diffraction
Molecules

ASJC Scopus subject areas

  • Materials Chemistry
  • Materials Science(all)

Cite this

Postintercalative polymerization of aniline and its derivatives in layered metal phosphates. / Liu, Yu Ju; Kanatzidis, Mercouri G.

In: Chemistry of Materials, Vol. 7, No. 8, 1995, p. 1525-1533.

Research output: Contribution to journalArticle

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N2 - 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 N-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.

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