Read e-book online Neodymium Based Ziegler Catalysts – Fundamental Chemistry PDF

By Lars Friebe, Oskar Nuyken, Werner Obrecht (auth.), Oskar Nuyken (eds.)

ISBN-10: 3642071120

ISBN-13: 9783642071126

L. Friebe, O. Nuyken, W. Obrecht: Neodymium established Ziegler/Natta Catalysts and their program in Diene Polymerization.- A. Fischbach, R. Anwander: Rare-Earth Metals and Aluminum Getting shut in Ziegler-type Organometallics.-

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Residual activities can be attributed to the fact that freshly precipitated NdX3 is activated by aluminum alkyls and forms an active species. Definitive proof for the activation of NdX3 by aluminum alkyls is the first generation of binary catalyst systems which are based on NdCl3 /AlR3 . The first study in which the molar ratio nX /nCe was systematically varied dates back to Throckmorton’s pioneering work in which he used the catalyst system Ce octanoate/TIBA/halide donor [34]. Throckmorton compared the performance of the halide donors: Et2 AlF, Et2 AlBr, Et2 AlCl, EtAlCl2 and Et2 AlI.

If Nd(BH4 )3 · (THF)3 is combined with a stoichiometric amount of MgBu2 catalyst activities are increased, control of molar masses is improved and poly(diene)s with a trans-1,4-content of up to 99% are obtained. [348, 349]. Heteroleptic Nd complexes with three different ligands (Cp∗ -type, diketiminate and boranate) are used for the preparation of BR with a high trans1,4-content. 4%. These effects are observed in the polymerization of IP [350]. The use of Nd-hydride-based catalyst systems is described in a patent filed by Phillips Petroleum Co.

By this replacement the microstructure of the resulting polymer is completely changed and poly(diene)s with high trans-1,4-contents are formed [235, 353, 354]. Another interesting aspect brought about by magnesium alkyl cocatalysis is the preparation of poly(butadiene) block copolymers which comprise cis-1,4- and trans-1,4building-blocks [355, 356]. According to Jenkins trans-1,4-specific polymerization is started by a MgR2 -containing Nd catalyst system. During the course of the polymerization a halide donor is added and diene insertion is switched to the cis-1,4-mode.

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Neodymium Based Ziegler Catalysts – Fundamental Chemistry by Lars Friebe, Oskar Nuyken, Werner Obrecht (auth.), Oskar Nuyken (eds.)


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