公开(公告)号：US06207130B1

公开(公告)日：2001-03-27

申请号：US09058587

申请日：1998-04-10

申请人： Aivaras Kareiva ,  Chuansheng Bai ,  Charles Jeffrey Harlan ,  D. Brent MacQueen ,  Andrew R. Barron ,  Ronald L. Cook

发明人： Aivaras Kareiva ,  Chuansheng Bai ,  Charles Jeffrey Harlan ,  D. Brent MacQueen ,  Andrew R. Barron ,  Ronald L. Cook

IPC分类号： C01F702

CPC分类号： C01F7/002 ,  B82Y30/00 ,  C01F7/04 ,  C01F7/16 ,  C01F7/30 ,  C01F17/0025 ,  C01G1/00 ,  C01G45/006 ,  C01G51/006 ,  C01P2002/32 ,  C01P2002/34 ,  C01P2002/52 ,  C01P2002/54 ,  C01P2004/64 ,  C07F5/069 ,  C07F15/025 ,  C07F15/045 ,  C07F15/065

摘要： A method has been developed for the solution-based metal exchange of carboxylato-alumoxanes [Al(O)x(OH)y(O2CR)z]n with a wide range of metal cations. Metal-exchanged carboxylato-alumoxanes are new, particularly those in which about 10% to about 50% or more of the Al ions are exchanged for other metal ions. Additionally, the carboxylic acid ligands can be stripped from the boehmite core of metal-exchanged carboxylato-alumoxanes at low temperature leading to the formation of metal-exchanged boebmite particles. These new material phases can be used as intermediates for preparation of mixed metal aluminum oxide materials. Thermolysis of the metal-exchanged carboxylato-alumoxanes or metal-exchanged boehmite particles results in doped aluminas (M/Al2O3), binary (MAlOx), ternary (MM′AlOx) and even more complex metal aluminum oxide compounds, where M and M′ are metal ions other than those of aluminum and are preferably those of Lanthanide metals or transition metals. The method allows preparation of pure phase materials as well as the preparation of metastable metal aluminum oxide phases. The carboxylato-alumoxanes are prepared by the reaction of boehmite (or pseudoboehmite) with carboxylic acids in a suitable solvent. Up to at least half of the aluminum cations in the boehmite lattice of the carboxylato-alumoxanes can be replaced by the reaction of metal acetylacetonates with the carboxylato-alumoxane in a suitable solvent. The metal exchange reaction can also be carried out by reaction with soluble metal salts. Reactions of boehmite with the metal acetylacetonates (or soluble metal salts) do not lead to the metal exchange reaction observed for the carboxylato-alumoxanes.

摘要翻译： 已经开发了用于宽范围的金属阳离子的羧基 - 铝氧烷[Al（O）x（OH）y（O 2 CR）z] n的基于溶液的金属交换的方法。 金属交换的羧基铝氧烷是新的，特别是其中约10％至约50％或更多的Al离子被交换为其它金属离子的那些。 此外，羧酸配体可以在低温下从金属交换的羧酸 - 铝氧烷的勃姆石芯中汽提，导致形成金属交换的勃姆沸石颗粒。 这些新材料相可以用作制备混合金属氧化铝材料的中间体。 金属交换的羧酸 - 铝氧烷或金属交换的勃姆石颗粒的热解导致掺杂的氧化铝（M / Al 2 O 3），二元（MA 1 O x），三元（MM'AlO x）和甚至更复杂的金属氧化铝化合物，其中M和M' 是除铝以外的金属离子，优选为镧系金属或过渡金属的金属离子。 该方法允许制备纯相材料以及制备亚稳态金属氧化铝相。 羧基铝氧烷通过勃姆石（或假勃姆石）与羧酸在合适溶剂中的反应来制备。 羧酸 - 铝氧烷的勃姆石晶格中的至少一半的铝阳离子可以通过金属乙酰丙酮化物与羧基 - 铝氧烷在合适的溶剂中的反应来代替。 金属交换反应也可以通过与可溶性金属盐反应来进行。 勃姆石与金属乙酰丙酮化物（或可溶性金属盐）的反应不会导致对羧基铝氧烷观察到的金属交换反应。