Ziegler type catalysts

From the time that isoprene was isolated from the pyrolysis products of natural mbber (1), scientific researchers have been attempting to reverse the process. In 1879, Bouchardat prepared a synthetic mbbery product by treating isoprene with hydrochloric acid (2). It was not until 1954—1955 that methods were found to prepare a high i i -polyisoprene which dupHcates the stmcture of natural mbber. In one method (3,4) a Ziegler-type catalyst of tri alkyl aluminum and titanium tetrachloride was used to polymerize isoprene in an air-free, moisture-free hydrocarbon solvent to an all i7j -l,4-polyisoprene. A polyisoprene with 90% 1,4-units was synthesized with lithium catalysts as early as 1949 (5). 

Polymerization of olefins such as styrene is promoted by acid or base or sodium catalysts, and polyethylene is made with homogeneous peroxides. Condensation polymerization is catalyzed by acid-type catalysts such as metal oxides and sulfonic acids. Addition polymerization is used mainly for olefins, diolefins, and some carbonyl compounds. For these processes, initiators are coordination compounds such as Ziegler-type catalysts, of which halides of transition metals Ti, V, Mo, and W are important examples. 

Polymerizations catalyzed with coordination compounds are becoming more important for obtaining polymers with special properties (linear and stereospecific). The first linear polyethylene polymer was prepared from a mixture of triethylaluminum and titanium tetrachloride (Ziegler catalyst) in the early 1950s. Later, Natta synthesized a stereoregular polypropylene with a Ziegler-type catalyst. These catalyst combinations are now called Zieglar-Natta catalysts. 

Polypropylene (PP) is a major thermoplastic polymer. Although polypropylene did not take its position among the large volume polymers until fairly recently, it is currently the third largest thermoplastic after PVC. The delay in polypropylene development may be attributed to technical reasons related to its polymerization. Polypropylene produced by free radical initiation is mainly the atactic form. Due to its low crystallinity, it is not suitable for thermoplastic or fiber use. The turning point in polypropylene production was the development of a Ziegler-type catalyst by Natta to produce the stereoregular form (isotactic). 

Zero point vibration, 235 Ziegler type catalyst, 162 Zinc-tin, alloy (Zn6Sn5), calculation of thermodynamic quantities, 136... 

Hydrosilylation by Ziegler-type catalyst systems [e.g., Ni(acac)2/AlEt3] has been examined for the reaction of 1-octene with EtjSiH in benzene 178). Complications include competing isomerization and reduction to metal however, 1,3-dienes or terminal acetylenes are readily hydrosilylated withRC i CH, the major product is CH2 CR. CRiCHSiXj. 

Review of recent literature on Ziegler-type catalysts... 

A stereo specific polymer produced by the copolymerisation of ethylene and propylene with Ziegler-type catalysts. 

Dimersol E A process for making gasoline from ethylene. The catalyst is a soluble Ziegler-type catalyst containing nickel. Developed by IFP in the 1980s and operated at an undisclosed location since 1988. 

Other examples of arene hydrogenation by Ziegler-type catalysts have been reported [35]. However, none of them is discussed at this point as they are generally poorly defined. Likewise, some hydrogenation catalytic systems in either oxo or water-gas-shift conditions are only reported in the list of references for sake of information [24, 36]. 

Ziegler-type catalysts obtained from an organic acid salt or acetylacetone salt of nickel, cobalt, iron, or chromium which reacts with a reducing agent such as an organic aluminum compound. 

Although Ziegler-type catalysts have been widely investigated for the homogeneous hydrogenation of polymers, their catalytic mechanism remains unknown. One possible reason for this may be the complexity of the coordination catalysis and the instability of the catalysts. Metallocene catalysts are highly sensitive to impurities, and consequently it is very difficult to obtain reproducible experimental data providing reliable kinetic and mechanistic information. 

Polypropylene is produced from the monomer propylene by using the Ziegler-type catalyst as in case of polyethylene. 

The Ziegler-type catalysts contain also a metal-alkyl, like triethylaluminum. They work usually at moderate temperature and pressure. The most active catalysts for polymer hydrogenation are the noble metal complex catalysts, and they can also be used for reduction of elastomers in the latex phase. The most difficult task is the removal of the catalyst from the reaction mixture. The methods used are based on extraction, adsorption, absorption or on their combination. 

Among group 8 transition metal catalysts, iron-based Ziegler-type catalysts such as Fe(acac)3-Et3Al(l 3) (acac = acetylacetonate) have been well known from the early stage of the catalyst investigation, which are readily prepared in situ to polymerize sterically unhindered terminal acetylenes such as -alkyl-, r f-alkyl-, and phenylacetylenes. The formed poly(phenylacetylene) has red color and r-cisoidal structure, and is insoluble and crystalline. 

A number of Ziegler-type catalysts based on early transition metals and tri-alkylaluminum or similar organometallic compounds are soluble in hydrocarbon solvents and function as homogeneous hydrogenation catalysts.24,26 Many of the... 

Ziegler-type catalysts based upon Co, Ni, and Fe and in the presence of aluminum alkyls codimerize butadiene with olefins such as ethylene,... 

The polymerization of butadiene to 1.2 polymers with anionic Ziegler type catalysts has been studied by Natta and co-workers (46). They have shown that isotactic 1.2-polybutadiene can be produced by the use of catalysts which are made up of components which have basic oxygen and nitrogen structures such as triethylaluminum with cobalt acetylacetonate or with chromium acetylacetonate. Natta and co-workers have shown that either syndiotactic or isotactic structures are produced depending on the ratio of aluminum to chromium. Syndiotactic structures are obtained at low aluminum to chromium ratios while isotactic polybutadiene is obtained at high ratios. The basic catalyst component is characteristic of syndiotactic catalysts. Natta, Porri, Zanini and Fiore (47) have also produced 1.2 polybutadiene using... 

Using diolefins and carefully selected Ziegler-type catalysts, it has been possible to obtain the 1,4-c/s-, the 1,4-trans-, and the 1,2-polybutadienes more than 98% pure. In the case of polyisoprene, the 3,4-structure is produced. There are thousands of patents involving every combination of pure or mixed main-group alkyls with transition-element compounds, each claiming advantages. However, compositions containing titanium, vanadium, chromium, and, in special cases, molybdenum, cobalt, rhodium, and nickel are primarily used. 

Many results obtained with diolefins can be explained in essentially the same way as for those with a-olefins. Nevertheless, there are some differences concerning observations made with T)3-allylnickel complexes and the influence of ligands on the results obtained by using Ziegler-type conditions (64). Some of these systems are far from being true Ziegler-type catalysts. Probably, the structural isomerism of polydienes depends essentially on the specific nature of the metal which forms a complex with the diene involved. 

For Ziegler-type catalysts based on titanium, we prefer the interpretation proposed by Cossee (65) and Arlman (66) this is based simply on monodentate-trans or bidentate-cis coordination of the diolefin which, respectively, gives a trans or cis configuration in the polymer produced (see Fig. 8). 

It should be mentioned that the supported Ziegler-type catalysts have... 

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