SYNTHESIS OF AMIDE-FUNCTIONALIZED AND ESTER-FUNCTIONALIZED ZIRCONIUM PHOSPHONATES

The syntheses of layered amide and ester derivatives of Zr(O3PCH2CH2COOH) are described. These new materials, Zr(O3PCH2CH2COXC(n)H2nH)2 (X = NH, n = 0-18; X = O, n = 2-6), are prepared via amine and alcohol intercalation reactions of layered Zr(O3PCH2CH2COCl)2. They are characterized by powder X-ray diffraction, IR, and C-13 CP MAS NMR spectroscopies as well as by thermogravimetric analysis. The interlayer separation in these materials is directly related to the length (n) of the amide or ester alkyl chain. For amides, the interlayer distance varies from 13.8 to 53 angstrom and is consistent with an angle of 59-degrees between the the alkyl chain and the surface of the inorganic layer. The layered amide compounds have greater thermal and chemical stabilities than analogous compounds prepared by Bronsted acid/base reactions. A bridging ester derivative, Zr(O3PCH2CH2COOCH2CH2CH2PO3), has also been prepared by the reaction of Zr(O3PCH2CH2COCl)2 with HSn(C4H9)3.