By Lars Friebe, Oskar Nuyken, Werner Obrecht (auth.), Oskar Nuyken (eds.)
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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Extra info for Neodymium Based Ziegler Catalysts – Fundamental Chemistry
According to these studies the catalyst system is highly active even at low nAl /nNd -ratios < 5 and polymerization rates decrease with increasing nAl /nNd -ratios within the nAl /nNd range = 5–50 (Sect. 10) . For the Nd-amide-based system Nd(N(SiMe3 )2 )3 /TIBA/DEAC polymerization rates show a maximum at nTIBA /nNd = 40 within the investigated range of nTIBA /nNd ratios 0–40 . The boranate system Nd(BH4 )3 (THF)3 /TEA exhibits a maximum at nTEA /nNd = 5 in the investigated range of nTEA /nNd = 5–50 .
Dong et al. studied the polymerization of IP with the catalyst system Nd(Oi Pr)3 /MMAO. Addition of the halide donors reduced catalyst activity in the following order: Et2 AlCl > t BuCl > Me3 SiCl . 4 Molar Ratio nCocatalyst /nNd Variations of the amount of cocatalyst which are usually expressed by the molar ratio nAl /nNd have a signiﬁcant inﬂuence on polymerization rates, molar masses, MMDs and on the microstructures of the resulting polymers. These aspects are addressed in the following sections with a special emphasis on ternary catalyst systems.
The upper organic phase contains Nd-carboxylate in a concentration of 38–46 wt. %. The water content of this phase reaches up to 20 000 ppm. The wet Nd-carboxylate containing solution is used without isolation of the Nd-carboxylate and without further puriﬁcation. The moisture containing solution is reacted with alkylaluminum 20 L. Friebe et al. or alkylaluminum hydride and organic halides under well-deﬁned conditions (0–18 ◦ C/> 30 min) [213–216]. In a similar method a well-deﬁned excess of water (nH2O /nNd ≥ 5/1) is applied in combination with an excess of carboxylic acid.
Neodymium Based Ziegler Catalysts – Fundamental Chemistry by Lars Friebe, Oskar Nuyken, Werner Obrecht (auth.), Oskar Nuyken (eds.)