Preparation and properties of the layered organic derivatives of γ-zirconium phosphate, Zr(CH3−(OCH2CH2)n−OPO3) (HPO4) (n=1–3)
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New kinds of organic derivatives of layer structured γ-zirconium phosphate Zr(HPO4)2·2H2O are prepared by the exchange of the interlayer phosphate groups with phosphoric ester groups having oxyethylene chains, CH3−(OCH2CH2)n−OPO32− (n=1–3). Half of the interlayer phosphate groups are exchanged topochemically, the oxyethylene chains being grafted onto the phosphate layers through the ester bonds in the resulting derivatives. The derivatives behave like crown ethers, and form complexes with alkali salts of soft base anions such as SCN− and I−. Alkali salts of hard base anions such as Br− and NO3− do not form complexes with the derivatives. The alkali iodide complexes of the organic derivatives can be used for the halogen exchange reaction. n-Butyl bromide is converted into n-butyl iodide in the presence of the alkali iodide complexes. The reactivities for the halogen exchange reaction increase with the number of the oxyethylene units.
KeywordsCrown Ether Base Anion Ester Bond Oxyethylene Phosphoric Ester
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