Environmentally Benign Immobilized Organometallic Acids

在这个环境友好的化学合成和加工项目中，在无机、生物无机和有机金属化学计划的支持下，学术化学家、犹他大学的John Gladysz教授和工业化学家、埃克森公司研究实验室的Istvan Horvath博士将承担新型固体酸催化剂的开发。这些酸催化剂将基于固定在固体聚合物载体上的质子型有机金属化合物，如聚苯乙烯和Nafion。预计这些酸将表现出新的反应模式，包括酸性质子和金属中心。这些努力的成功可能会导致产生比目前方法更少的酸性废物的工艺。有机金属酸的固定化将需要开发新的配体和将其连接到聚合物载体上的方法。聚苯乙烯将被氟化的多齿有机膦或环戊二烯配体衍生化，这些配体将用于结合金属氢化物物种。替代系统将以Nafion为基础，Nafion已在磺胺基团与给体基团衍生化，使金属氢化物物种可以共价结合。新的组合物将通过红外和核磁共振光谱、Hammett酸度的测量以及对烷基化反应(如石油原料转化所需的反应)中的催化活性进行筛选来表征。大多数已知的工业化学制造过程都涉及到某种类型的催化。这些催化过程中有大量涉及到强酸的使用。使用可溶性酸的那些通常会产生大量的高酸性废物，必须在处置之前对其进行处理以降低其酸度。可以取代这些的新的固相酸是非常可取的。该项目对新材料进行基础研究，最终为更环保地生产重要的商品化学品奠定基础。

In this Environmentally Benign Chemical Synthesis and Processing project, supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program, academic chemist, Professor John Gladysz of the University of Utah and industrial chemist, Dr. Istvan Horvath of Exxon Corporate Research Laboratory will undertake the development of new solid acid catalysts. These acid catalysts will be based upon protic organometallic compounds immobilized on solid polymeric supports such as polystyrene and Nafion. It is expected that these acids will exhibit new modes of reactivity that will involve both the acidic proton and the metal center. Success in these endeavors could result in processes that produce less acidic wastes than current methods. Immobilization of the organometallic acids will require the development of new ligands and methods for attaching them to the polymeric supports. Polystyrene will be derivatized with fluorinated polydentate organophosphine or cyclopentadienyl ligands, which will be used to bind metal hydride species. Alternative systems will be based upon Nafion, which has been derivatized at the sulfonamide group with donor groups such that metal hydride species can be covalently bound. New compositions will be characterized by infrared and NMR spectroscopies, by measurements of Hammett acidities, and by screening for catalytic activity in alkylation reactions such as those that are required for petroleum feedstock conversions. The majority of known industrial chemical manufacturing processes involve some type of catalysis. A large number of these catalytic processes involve the use of strong acids. Those that employ soluble acids often generate large quantities of highly acidic waste that must be treated to reduce its acidity prior to disposal. New solid-phase acids that may replace these are highly desirable. This project undertakes fundamental studies of new materials that ultimate provide the basis for more environmentally benign manufacture o f important commodity chemicals.