Metallocene catalysis syndiotactic

Polypropylenes produced by metallocene catalysis became available in the late 1990s. One such process adopts a standard gas phase process using a metallocene catalyst such as rac.-dimethylsilyleneto (2-methyl-l-benz(e)indenyl)zirconium dichloride in conjunction with methylaluminoxane (MAO) as cocatalyst. The exact choice of catalyst determines the direction by which the monomer approaches and attaches itself to the growing chain. Thus whereas the isotactic material is normally preferred, it is also possible to select catalysts which yield syndiotactic material. Yet another form is the so-called hemi-isotactic polypropylene in which an isotactic unit alternates with a random configuration. 

Because of the chain-stiffening effect of the benzene ring the TgS of commercial materials are in the range 90-100°C and isotactic polymers have similar values (approx. 100°C). A consequence of this Tg value plus the amorphous nature of the polymer is that we have a material that is hard and transparent at room temperature. Isotactic polystyrenes have been known since 1955 but have not been of commercial importance. Syndiotactic polystyrene using metallocene catalysis has recently become of commercial interest. Both stereoregular polymers are crystalline with values of 230°C and 270°C for the isotactic and syndiotactic materials respectively. They are also somewhat brittle (see Section 16.3). 

The active site in chain-growth polymerizations can be an ion instead of a free-radical. Ionic reactions are much more sensitive than free-radical processes to the effects of solvent, temperature, and adventitious impurities. Successful ionic polymerizations must be carried out much more carefully than normal free-radical syntheses. Consequently, a given polymeric structure will ordinarily not be produced by ionic initiation if a satisfactory product can be made by less expensive free-radical processes. Styrene polymerization can be initiated with free radicals or appropriate anions or cations. Commercial atactic styrene polymers are, however, all almost free-radical products. Particular anionic processes are used to make research-grade polystyrenes with exceptionally narrow molecular weight distributions and the syndiotactic polymer is produced by metallocene catalysis. Cationic polymerization of styrene is not a commercial process. 

In syndiotactic or syntactic macromolecules, the substituents have alternate positions along the chain (Figure 20.1). The macromolecule consists of 100% racemo diads. Syndiotactic polystyrene (sPS), made by metallocene catalysis polymerization, is crystalline with a melting temperature of 161°C. 

With the advent of metallocene catalysis, a range of tacticities and structures are possible see Figure 14.2 (4). Thus a range of compositions not easily prepared before, such as syndiotactic, hemi-isotactic, and isoblock copolymers, are now possible. 

Syndiotactic polystyrene is produced using metallocene catalysis and, unlike the atactic polymer, is highly crystalline with a of270°C. Most grades offered are glass-... 

Work in the application of metallocene-based catalysis to olefin polymers has become a research topic of growing interest in recent years. A great number of symmetrie and chiral zirconocenes have been synthesized to give totally different structures of isotactic, syndiotactic, atactic or block polymers. The isotactic sequence length of polypropylene is influenced by the nature of the ligands of the metallocene. New ring or bridge substituted metallocene/methylalumoxane catalysts for the olefin polymerization are described. 

Industrial applications of metallocene catalysts are a recent development AU of them possess in their reaction center two aromatic rings, between which a complex bond holds a metal atom, in most cases zirconium. This type of catalysis produces polymers with exceptionally uniform structures. The chain lengths of the individual molecules closely approximate one another. The spatial structure is therefore well-defined. Polypropylene, for instance, is completely isotactic. It is even possible to produce polypropylene in which the pendant group orientation alternates between right and left. The resulting substance is known as a syndiotactic polypropylene (see above) [3]. 

Although at present most of the production of iPP uses Ziegler-Natta catalysis, one can expect that metallocene-containing systems will be more used. Their high efficiency and the possibilities they offer in the fine control of the tactic-ity of poly(a-olefins) make them increasingly attractive. In particular, syndiotactic polypropylene (sPP) could be obtained under industrial conditions. This material is different from iPP. 

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