【作者】 杨新斌；

【导师】 傅相锴；

【作者基本信息】 西南师范大学 ， 应用化学， 2005， 硕士

【摘要】 磷酸氢锆{α-Zr（HPO₄）₂·H₂O（简称α-ZrP）和γ-Zr（PO₄）（H₂PO₄）·2H₂O（简称γ-ZrP）}、磷酸氢锆衍生的有机膦酸锆以及无机-有机混合膦酸锆是一类层状结构化合物,主要用作离子交换剂、催化剂及催化剂载体、吸附剂和色谱填充剂等。近年来以磷酸氢锆及其衍生物作主体,一些客体分子克服层与层之间的相互作用力可逆地插入到层间空隙,将层板撑开,层间距扩大,主-客体之间通过离子键、氢键、范德华力等作用力组装成具有特殊结构的复合材料,它们在离子交换、吸附、催化、医药、电化学、光化学、生物、环保等领域有广阔的应用前景。这类特殊结构的复合材料具有三个显著特点:第1,制备条件温和,通常在室温、水或醇等溶液中进行;第2,通过对主体分子的设计,提高对客体分子的选择性,可以得到预先设计分子结构的复合材料;第3,通过对一些功能性客体分子进行插层组装,可以得到具有光、电、磁等结构新颖的复合材料。 设计新型功能主体分子以改变对客体分子的识别能力从而改变插层复合材料的性能是主-客化学的一个重要研究领域。我们利用α-ZrP结构的规整性、可设计性和有机合成化学的丰富多样性,将含有-COOH、-SO₃H或长链烷基等功能基团的有机双膦酸部分或全部代替α-ZrP层板上的羟基,由于这类混合磷酸锆既保留了无机α-ZrP的层状结构特点,同时又具有有机基团的大小和含量比可根据需要进行设计等优点,并且由于双膦酸的立体几何特性,它的2个膦酸基团连在锆层板的同一层,两个相邻有机基团的距离比α-ZrP的两个相邻-OH的距离增大了一倍,横向可利用空间较大,因此可获得具有与α-ZrP不同的反应活性和可控制微环境的新型主体,以改变对客体分子的插层性能,制备出性能独特的复合层状材料,目前这方面的研究在国内外报道比较少。 用Mannich方法合成三种有机双膦酸,用红外光谱（IR）、核磁共振氢谱（¹HNMR）和核磁共振磷谱(³¹PNMR)对其结构进行了表征。 报道了不同x值（x=2.00、1.50、1.34、1.00、0.66、0.50）的层状（甘氨酸-N,N-双甲基膦酸-磷酸氢）锆{Zr[（O₃PCH₂）₂NCH₂COOH]_x/2（HPO₄）_2-x·nH₂O)的制备,并成更多还原

【Abstract】 Zirconium phosphates, zirconium phosphonates and zirconium phosphate-phosphonate are a kind of multifunctional materials that can be used as ion-exchangers, catalysts or catalyst supports, absorbents and chromatogram filling. In recent years, much attention has been paid to the intercalation behavior of zirconium phosphate and its derivatives, some guests are intercalated into zirconium phosphate and its derivatives by ion bond, hydrogen bond and so on between host and guest in order to prepare general structural intercalation complex materials that are extensively applied in many fields such as ion-exchanger, adsorbentt catalyst, medication, electrochemistry, biology, photochemistry, envioniment and like. This kind of general structural intercalation complex materials have three obvious characteristics: i) Conditions of intercalation reaction are wild in room temperature, water or ethanol solution usually, ii) we can process molecule design of host for increasing selectivity to guest molecules in order to prepare general structural intercalation complex materials, iii) we can obtain all kinds of applied purpose complex materials by intercalating different functional guests.Research on intercalation chemistry is extensively active in designing new type hosts. Because of the regularity and designability of structure of a - zirconium phosphate and the variety of organic synthesis, -OH group of a - zirconium phosphate are replaced by dimethylphosphonate with -COOH, -SO3H and an alkyl group with a long chain, and diphosphonate groups are bonded to metal atom on the same side of the layers due to the geometrical features of the diphosphonate moieties. The zirconium diphosphonates with half of the organic groups have more available transverse space in interlayer region than a -zirconium phosphate , therefore we can obtain different reactive and controlled microenvironment hosts that are different from a — zirconium phosphate , this aspect has been reported seldom at present.更多还原