Ziegler-Natta catalyst system

Before the development of the Ziegler-Natta catalyst systems (Section 6 21) polymer ization of propene was not a reaction of much value The reason for this has a stereo chemical basis Consider a section of polypropylene... 

Coordination polymerization of isoprene using Ziegler-Natta catalyst systems (Section 6 21) gives a material similar in properties to natural rubber as does polymerization of 1 3 butadiene Poly(1 3 buta diene) is produced in about two thirds the quantity of SBR each year It too finds its principal use in tires... 

Catalysts. Iodine and its compounds ate very active catalysts for many reactions (133). The principal use is in the production of synthetic mbber via Ziegler-Natta catalysts systems. Also, iodine and certain iodides, eg, titanium tetraiodide [7720-83-4], are employed for producing stereospecific polymers, such as polybutadiene mbber (134) about 75% of the iodine consumed in catalysts is assumed to be used for polybutadiene and polyisoprene polymeri2a tion (66) (see RUBBER CHEMICALS). Hydrogen iodide is used as a catalyst in the manufacture of acetic acid from methanol (66). A 99% yield as acetic acid has been reported. In the heat stabiH2ation of nylon suitable for tire cordage, iodine is used in a system involving copper acetate or borate, and potassium iodide (66) (see Tire cords). 

Factors affecting laboratory polymerisation of the monomer have been discussed" and these indicate that a Ziegler-Natta catalyst system of violet TiCl3 and diethyl aluminium chloride should be used to react the monomer in a hydrocarbon diluent at atmospheric pressure and at 30-60°C. One of the aims is to get a relatively coarse slurry from which may be washed foreign material such as catalyst residues, using for example methyl alcohol. For commercial materials these washed polymers are then dried and compounded with an antioxidant and if required other additives such as pigments. 

Polybutadiene was first prepared in the early years of the 20th century by such methods as sodium-catalysed polymerisation of butadiene. However, the polymers produced by these methods and also by the later free-radical emulsion polymerisation techniques did not possess the properties which made them desirable rubbers. With the development of the Ziegler-Natta catalyst systems in the 1950s, it was possible to produce polymers with a controlled stereo regularity, some of which had useful properties as elastomers. 

Polymers containing 90-98% of a c 5-1,4-structure can be produced using Ziegler-Natta catalyst systems based on titanium, cobalt or nickel compounds in conjuction with reducing agents such as aluminium alkyls or alkyl halides. Useful rubbers may also be obtained by using lithium alkyl catalysts but in which the cis content is as low as 44%. 

The polyalkenamers are usually prepared by means of a Ziegler-Natta catalyst system. For example fran.v-polypentenamer may be obtained from cyclopentene... 

Attempts to produce coplymers of ethylene and styrene by free radical and by conventional Ziegler-Natta catalysts systems have, over the years, not proved successful. However, in 1998 Dow announced novel polymers using a metallocene process with the intention of commercial polymerisation using a 23 000t.p.a. capacity plant starting in 1999. 

Polymers manufactured via single site catalyst technologies, because of the unique chemical catalytic environment, exhibit a more controlled molecular weight distribution and tacticity than seen with Ziegler-Natta catalyst systems. 

By performing excellent model reactions [144], Grubbs and his co-workers demonstrated direct olefin insertion into an M-C bond. Thus, complex 115 was treated with AlEtCl2 to give complex 116, whose decomposition afforded methylcyclopentane. Under the same conditions, the polymerization of ethylene took place. In this way, the insertion of a-olefins into a Ti-C single bond in a model Ziegler-Natta catalyst system was directly observed (Eq. 9). 

The catalytic cyclo-oligomerization of 1,3-butadiene mediated by transition-metal complexes is one of the key reactions in homogeneous catalysis.1 Several transition metal complexes and Ziegler-Natta catalyst systems have been established that actively catalyze the stereoselective cyclooligomerization of 1,3-dienes.2 Nickel complexes, in particular, have been demonstrated to be the most versatile catalysts.3... 

Metallocenes give polyethylene producers a long list of opportunities to work on. They have already created polyethylene copolymers that compete well in applications that have been formerly the exclusive domain of the more costly, so-called high value plastics. Further, they are augmenting the chromium oxide and Ziegler-Natta catalysts systems that have been used for HDPE and LLDPE with metallocene catalysts. That creates even further... 

Ziegler-Natta Catalysts. All isotactic polymers of higher a-olefins are produced with the same type of heterogeneous, titanium-based Ziegler-Natta catalyst systems as that used for the manufacture of isotactic PP. 

The copolymerization of propylene with allyldimethylsilane (ADMS) was carried out with Ziegler-Natta catalyst systems supported on MgC. The obtained PP-g-ADMS was treated with SOCI2 to produce PP-g-Cl, which works as a macroinitiator for ATRP. PP-g-PMMA (Mn = 67 700, Mw/Mn = 5.3, PMMA segment 79.6 wt%) was produced from PP-Si-Cl with MMA and CuCl/PMDETA [77],... 

The reactions between TiCl4 and AlMe3 are of particular interest in studies of olefin-polymerization catalysts as a Ziegler-Natta catalyst system.14 The reaction between a surface TiClx group and AlMe3 gas is known to give an active olefin polymerization catalyst.1... 

B. The (Butadiene)zirconocene Route to Active Ziegler-Natta Catalyst Systems... 

Butadiene)zirconocenes, 109-162 active Ziegler-Natta catalyst systems, 142-149... 

The type of solvent or diluent should be specified in reporting a Ziegler-Natta catalyst system. Alkene polymerisations are usually carried out in inert solvents, such as aliphatic or aromatic hydrocarbons (e.g. some gasoline fractions or toluene). The use of protic or aprotic polar solvents or diluents instead of the hydrocarbon polymerisation medium can drastically alter the reaction mechanism. This usually results in catalyst deactivation for alkene coordination polymerisation. Modern alkene polymerisation processes are carried out in a gas phase, using fluidised-bed catalysts, and in a liquid monomer as in the case of propylene polymerisation [28,37]. 

In discussions about the nature of the active species in the polymerization of dienes by Ziegler/Natta catalyst systems allyl species have already been suggested in the 1960s [273-278]. This discussion has continued through the past decades [139,279-283]. Today, it is widely accepted that Nd-allyl-groups are the key element in the insertion of dienes into the Nd carbon bond. 

In the polymerization of dienes with Ziegler/Natta catalyst systems it is a well-established fact that the presence of halide donors is essential in order to achieve high catalytic activities and high cis-1,4-contents [360,361]. The halide free catalyst system NdO/TIBA is a good example for a catalyst with a poor performance and a high trans- 1,4-specificity [362,363]. For various binary and ternary catalyst systems the qualitative impact of chlorides on the stereochemistry of BR is demonstrated in a series of fundamental experiments the results of which are summarized in (Table 5) [364],... 

Beside the homopolymerization of BD Nd-based Ziegler/Natta catalyst systems are also applied for the homopolymerization of IP, the copolymerization of the dienes BD and IP, the homopolymerization and copolymerization of substituted dienes as well as for the copolymerization of BD with alkenes such as styrene, ethylene and other ethylene derivatives. 

As discussed in Sects. 2.1 and 2.2.8 control of molar mass is an important aspect in the large-scale polymerization of dienes. In Nd-catalyzed polymerizations the control of molar mass is unique amongst Ziegler/Natta catalyst systems as standard molar mass control agents such as hydrogen, 1,2-butadiene and cyclooctadiene which are well established for Ni- and Co-systems do not work with Nd catalysts [82,206,207]. The only known additives which allow for the regulation of molar mass without catalyst deactivation are aluminum alkyls, magnesium alkyls, and dialkyl zinc. 

In ternary Nd Ziegler/Natta catalyst systems of the type Nd compound/cocatal-yst/halide donor Al alkyl cocatalysts yield high czs-l,4-BR whereas Mg alkyl cocatalysts yield fra s-l,4-poly(butadiene). To date, it is not clear why the use of these two classes of co catalysts leads to completely different polymer microstructures. 

Table 30 Product features of high cis- 1,4-BR obtained with Ziegler/Natta catalyst systems...

HDPE is produced mainly by a suspension (slurry) process in various types of reactors and with various polymerization procedures. In these processes, a supported Ziegler-Natta catalyst system or a Phillips catalyst in a solvent is used. Because the temperature (80-100°C) is lower than the melting point of the polyethylene (140°C), the polymer produced is separated as a solid. This process is highly versatile and can be used to produce many kinds of polyethylenes. 

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