Olefinpolymerisation mittels Metallocenkatalysatoren

Werner Kaminsky
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引用次数: 42

Abstract

Metallocenes have gained widespread interest as catalysts for olefin polymerization due to their high activity and versatility. A large range of new polymers with narrow molecular weight distribution and different microstructures can be produced with these “single-site” catalysts. These highly active catalysts which are able to produce 40 tonnes of polyethylene per gram zirconium per hour are even capable of incorporating remarkable amounts of sterically demanding olefins and dienes in copolymerization with ethylene. Isotactic, syndiotactic, stereoblock and isoblock polyolefins are accessible by variation of the metallocene ligands. Similarly, the isotacticity and molecular weight of the generated polyolefins are influenced by the ligand structure. By heterogenization of the metallocene on metal powder or silica polymers with substantially higher molecular weight, higher melting points and other new properties may be attained. Cyclic olefins like cyclopentene, norbornene or dimethanooctahydronaphthalene polymerize without ring-opening to yield highly melting and poorly soluble polymers. By separation of the racemic catalyst into enantiomers, optically active alkanes and alkenes are accessi-ble. Trimers are obtained with ee of 95%. These results provide new insights into the mechanism of Ziegler-Natta catalysis.
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茂金属作为烯烃聚合催化剂因其高活性和多功能性而受到广泛关注。这些“单位点”催化剂可以生产出大量分子量分布窄、微观结构不同的新型聚合物。这些高活性催化剂每克锆每小时能够生产40吨聚乙烯,甚至能够将大量要求立体的烯烃和二烯与乙烯共聚。等规聚烯烃、共规聚烯烃、立体嵌段聚烯烃和等嵌段聚烯烃可通过茂金属配体的变化而得到。同样,合成的聚烯烃的等规性和分子量也受配体结构的影响。通过金属粉末或硅聚合物上的茂金属异质化,可以获得更高的分子量,更高的熔点和其他新的性能。环烯烃如环戊烯、降冰片烯或二甲基八氢萘聚合时不开环,产生高熔点和难溶性聚合物。通过将外消旋催化剂分离成对映体,可以得到具有光学活性的烷烃和烯烃。三聚体的ee为95%。这些结果为Ziegler-Natta催化的机理提供了新的认识。
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