Neodymium-halide-based systems

The usual cocatalysts for the activation of Nd-alcoholates comprise common aluminum alkyls, alumoxanes and magnesium alkyls which have already been described for the activation of the Nd halides (Sect. 2.1.1.1) and Nd carboxylates (Sect. 2.1.1.2) AlMe3 (TMA) [185,234], TIBA [224,225, 229,230], DIBAH [226,227,232], MAO [232,246], modified methyl alumox-ane (MMAO) [231] and MgR2 [235]. The ratios of cocatalyst/Nd-alcoholate are comparable with those described for the activation of Nd carboxylates. Table 4 gives a selection of catalyst systems based on neodymium alcoholates. 

Evans et al. sequentially reacted the Nd carboxylate precursor Nd[C>2CC (CH3)2CH2CH3]3 % first with DEAC and then with TIBA. By this reaction catalytically active systems are obtained which polymerize IP. In the first reaction step in which Nd carboxylate is reacted with DEAC mixed ligand complexes are formed which contain neodymium and aluminum as well as halide and ethyl groups. Upon crystallization NdC -based compounds are obtained in which solvent is coordinated. These compounds exhibit a more complex... 

Numerous binary and ternary diene polymerization initiator systems with neodymium as the rare-earth metal component have been designed empirically and investigated since the early discoveries in the 1960s. Commercially used neodymium-based catalysts mostly comprise Nd(III) carboxylates, aluminum alkyl halides, and aluminum alkyls or aluminum alkyl hydrides [43, 48,50-52]. Typically, the carboxylic acids, which are provided as mixtures of isomers from petrochemical plants carry solubilizing aliphatic substituents R. They are treated with the alkylaluminum reagents to generate the active catalysts in situ (Scheme 11). 

The f-transition metal catalysts were first described by von Dohlen [98] in 1963, Tse-chuan [99] in 1964 and later by Throckmorton [100]. In the 1980s Bayer [14] and Enichem [101] developed manufacturing processes based on neodymium catalysts. The catalyst system consists of three components [102] a carboxylate of a rare earth metal, an alkylaluminum and a Lewis acid containing a halide. A typical catalyst system is of the form neodymium(III) neodecanoate/diisobutylaluminum hydride/butyl chloride [103]. Neodymium(III) neodecanoate has the advantage of very high solubility in the nonpolar solvents used for polymerization. The molar ratio Al/Nd/Cl = 20 1 3. Per 100 g of butadiene, 0.13 mmol neodymium(III) neodecanoate is used. With respect to the monomer concentration, the kinetics are those of a first-order reaction. 

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