Procatalyst

Aluminum chloride dissolves readily in chlorinated solvents such as chloroform, methylene chloride, and carbon tetrachloride. In polar aprotic solvents, such as acetonitrile, ethyl ether, anisole, nitromethane, and nitrobenzene, it dissolves forming a complex with the solvent. The catalytic activity of aluminum chloride is moderated by these complexes. Anhydrous aluminum chloride reacts vigorously with most protic solvents, such as water and alcohols. The ability to catalyze alkylation reactions is lost by complexing aluminum chloride with these protic solvents. However, small amounts of these "procatalysts" can promote the formation of catalyticaHy active aluminum chloride complexes. 

Methods for identifying additional Ziegler-Natta co-catalysts in a catalyst system containing procatalysts magnesium and titanium are described by Campbell et al. (4). 

Research Focus Method for preparing poly(propene-l-butene-l-hexene) using a silyl/ zirconium-based Ziegler-Natta procatalyst. 

Semicrystalline poly(ethylene-co-propylene) was prepared by the authors (1) using a Zr/Si procatalyst, (I), supported on an organic porous substrate having pore sizes of 0.1 and 2 xm. The catalyst was prepared after activating... 

The preparation of poly (1-butene) containing isotactic pentads using procatalyst... 

A remarkable complex (33) with a C2-symmetric semicorrin ligand has been recently developed by Pfaltz and coworkers.64 A copper(II) complex was used as a procatalyst, but (33) was shown to be the active cyclopropanation catalyst. As shown in Table 3, this complex resulted in spectacular enantioselecti-vities in the range of 92-97% ee. Once again, the (15,35,4/ )-menthyl group attenuated the selectivity. Unfortunately, even though respectable yields were obtained with dienes and styrenes, the reaction with 1-heptene was rather inefficient. 

Three types of experiments have proved informative in the mechanistic study of asymmetric hydrogenation. These are, respectively, rate measurements and product analysis, X-ray crystallography and NMR-derived identification of stable and transient species involved in the catalytic cycle. The first two of these have been reviewed elsewhere (2, 3, 4) our own work has been concerned with NMR and has provided a surprising wealth of structural and mechanistic detail. A variety of chiral phosphine procatalysts have been used but the current discussion will be concerned largely with two. Thus (R,R)-1,2-ethanediylbis-[(2-methoxyphenyl)phenylphosphine] (1) (DiPAMP)... 

Ziegler-Natta catalysts are defined as the products formed in reactions of transition metal compounds of groups 4 to 8 (procatalysts, catalyst precursors) with organometallic compounds or metal hydrides of groups 1 to 4 (activators). These reactions are carried out in an inert medium and under inert (anaerobic) conditions ... 

Finally, most of the MgCl2-supported Ziegler-Natta catalysts for propylene polymerisation also require treatment of the supported procatalyst with... 

Nevertheless, many vanadium-based catalysts and polymerisation systems comprising them have received much academic attention in the hope that they might provide models for heterogeneous catalysts and polymerisation systems, since the problems connected with surface properties and particle size were believed to have been overcome. It must be noted, however, that homogeneous vanadium-based catalysts appeared to be more complex than was thought. There is no decisive evidence on the structure of catalytic sites formed by reaction between the procatalyst and activator. 

In connection with the above characteristic features of metallocene methy-laluminoxane catalysts, it must be emphasised that alternative, potentially cheaper alkylaluminoxanes, such as ethyl or z-butyl derivatives, which are more soluble in aliphatic hydrocarbons than methylaluminoxane, or other alkylaluminium compounds used as activators for metallocene procatalysts, show inferior activity. 

During the last decade, a variety of new catalysts have been presented for the stereospecific polymerisation of a-olefins, based on non-bridged metallocene or stereorigid ansa-metallocene as the procatalyst and a methylaluminoxane activator [29,30,37,105-107,112-114,116-135], Apart from isotactic [118,119,124, 131,132] and syndiotactic [23,118,124,133] polypropylenes and other poly(a-olefin)s [121], hemiisotactic [112,121,124], isoblock [131,132,134], syndioiso-block (stereocopolymer) [127], stereoblock isotactic [135] and stereoblock isotactic atactic [116,128,129] polypropylenes have been obtained using these new catalysts. 

The symmetry of the metallocene and also the kind of procatalyst metal atom, the nature of the catalyst activator and the polymerisation temperature determine the polypropylene tacticity. The general stereoregulation behaviour of metallocene catalysts may be explained in terms of the local chirality, or chirotopicity, of the catalytic sites bonded to the same metal atom. For this analysis, the structure of metallocenes as catalysts should be considered. 

The range of polypropylene microstructures available by procatalyst ligand (and/or metal) variation in the metallocene-methylaluminoxane system is illustrated in Table 3.1 [22,23,101,105,107,112,113,124,127,132,137], The ligands shown in Table 3.1, representative of the particular symmetry and class of the catalyst, are given as examples only. There are a variety of other metallocenes that have been successfully used to obtain polypropylenes of various stereostructures. 

Table 3.1 Relationship between the kind of bent metallocene procatalyst and the polypropylenex microstructure... 

In the case of propylene polymerisation with class III catalysts based on rac.-dimethylsilylenebis[l-(3-methylcyclopentadienyl)]zirconium dichloride [rac.-Me2Si(MeCp)2ZrCl2] (Table 3.1) or rac.-dimethylsilylenebis[l-(3-methyl-cyclopentadienyl)]hafnium dichloride [rac.-Me2Si(MeCp)2HfCl2] as a procatalyst, isoblock polypropylene is obtained [132]. 

Table 3.2 Non-bridged bent metallocene procatalysts and the polypropylene microstructures...

Figure 3.10 Monocyclopentadienyl amidotitanium procatalyst, dimethylsilylene(l -tetra -methylcyclopentadienyl)( -butyl)amidotitanium dichloride (Me2Si(Me4Cp)N( -Bu) TiCE, for obtaining low-density polyethylene. Front side view and side view respectively...

For the majority of olefin polymerisations with heterogeneous Ziegler Natta catalysts, the polymerisation rates, Rv, are proportional to the concentrations of procatalyst (MtX ) and monomer (M), but do not depend on the concentration of alkylaluminium activator (A) as long as a threshold concentration is maintained [37] ... 

This means that there is practically no dependence of the olefin polymerisation rate on the activator/procatalyst molar ratio over a wide range. In some... 

Figure 3.39 Chiral procatalyst of C2 symmetry containing two -substituents at the cyclopentadienyl rings, rac.-ethylenebis[l-(3-methylindenyl)]zirconium dichloride [rac.-(MeIndCH2)2ZrCl2], which, in combination with [Al(Me)o]x, produces atactic polypropylene. Front side view and side view respectively...

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