Postintercalative Polymerization of Aniline and Its Derivatives in Layered Metal Phosphates

Yu Ju Liu; Mercouri G. Kanatzidis

doi:10.1021/cm00056a019

Postintercalative Polymerization of Aniline and Its Derivatives in Layered Metal Phosphates

Yu Ju Liu, Mercouri G. Kanatzidis^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

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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 language	English (US)
Pages (from-to)	1525-1533
Number of pages	9
Journal	Chemistry of Materials
Volume	7
Issue number	8
DOIs	https://doi.org/10.1021/cm00056a019
State	Published - Aug 1995

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General Chemistry
General Chemical Engineering
Materials Chemistry

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@article{235748b297ef4bd9a7a6e5dd7fa5f3fd,

title = "Postintercalative Polymerization of Aniline and Its Derivatives in Layered Metal Phosphates",

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 {\AA} for anilinium/uranyl phosphate but dramatically decreases from 28.3 to 20.5 {\AA} for PPDA/Zr(HOPO3)2 and from 18.87 to 13.25 {\AA} 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.",

author = "Liu, {Yu Ju} and Kanatzidis, {Mercouri G.}",

year = "1995",

month = aug,

doi = "10.1021/cm00056a019",

language = "English (US)",

volume = "7",

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journal = "Chemistry of Materials",

issn = "0897-4756",

publisher = "American Chemical Society",

number = "8",

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AU - Liu, Yu Ju

AU - Kanatzidis, Mercouri G.

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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 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.

AB - 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.

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Postintercalative Polymerization of Aniline and Its Derivatives in Layered Metal Phosphates

Abstract

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