Neodymium-based butadiene

A common feature of catalysts based on 4 and 5f block elements is that of being able to polymerize both butadiene and isoprene to highly cistactic polymers, independently of the ligands involved. Butadiene, in particular, can reach a cistacticity as high as 99% with uranium based catalysts (3) and cistacticity of > 98% with neodymium based catalysts (4). This high tacticity does not change with the ligand nature (Fig. 1) in contrast to conventional catalysts based on 3-d block elements. A second feature of f-block catalysts is that the cis content of polymer is scarcely... 

Si02-supported neodymium-based catalyst mixtures Nd(naph)3/Al2Et3Cl3/ A1( Bu)3 (54) and Al( Bu)2H (DIBAH), instead of Al( Bu)3, were also tested as initiators for the gas-phase polymerization of 1,3-butadiene by varying the polymerization temperature, nature and feed of co-catalyst and polymerization time (Table 12.8). High ds-1,4-contents (97.8-98.9%) and activities between 400 and 2300 kg-PBD molNd h bar were observed, but the polymers displayed broad molecular weight distributions of 2 < M /M < 8 [158-160]. 

Scheme 29 Polymerization of butadiene by 1,2- and 1,4-insertion with neodymium-based Ziegler/Natta-catalysts (charge and ligands of neodymium are omitted for clarity)...

Scheme 51 Stereospecific butadiene polymerization based on a MMAO-activated neodymium methyl complex supported by a dianionic modification of neutral 2,6-diimino-pyridine [190]...

Neodymium-based Ziegler-Natta systems play a major role in the industrial polymerization of 1,3-butadiene to poly-cw-1,4-butadiene [182-184]. Therefore, the catalytic activity of the neodymium complex 229 was investigated for the polymerization of 1,3-butadiene [181]. The observed catalytic... 

This gives rise to dual valency state (+3 and +4) (23). As to the activity of lanthanide based catalysts we confirm a singular behavior that has been already reported by Chinese scientists (22) and that is summarized in Fig. 9. The activity of lanthanides in promoting the polymerization of butadiene and isoprene shows a large maximum centered on neodymium, the only exception being represented by samarium and europium that are not active, reasonably because they are reduced to bivalent state by aluminum alkyls, as pointed out by Tse-chuan and associates (22). 

Beyond this exclusive lanthanide Ziegler-Natta model, Ziegler-type multicomponent systems ( Mischkatalysatoren ) represent the only class of homogeneous rare-earth metal catalysts of considerable commercial relevance [40-43]. High-czs-1,4-polydienes are industrially produced from 1,3-dienes (butadiene and isoprene) in aliphatic or aromatic hydrocarbons by a number of Mischkatalysatoren based on the transition metals titanium, cobalt, and nickel, and the lanthanide element neodymium [40-47]. The... 

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. 

Polymerization of butadiene with Ziegler-Natta catalyst systems based on neodymium. Quimia Nova 2004,27, 111. 

Figure 3.9 Stereospecific polymerisation of isoprene (2-methyl-butadiene-l,3). The Russian industry has implemented technologies of c/s-l,4-polyisoprene synthesis with Ti-Al Ziegler-Natta catalysts (synthetic c/s-isoprene rubber SKI-3) and neodymium salts-based lanthanide catalysts SKI-5 grade synthetic rubber (TU 2294-051-16810126-96). SKI-3 rubbers contain up to 93 1% of as-1,4 links, while their content in SKI-5 grade rubber is 96 1%...

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