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A variety of different compounds have been added to recipes for Ziegler Natta initiators in attempts to enhance stereoselectivity and activity [Boor, 1979; Coover et al, 1967] These are electron donors (Lewis bases) and include oxygen, water, inorganic and organic halides, phenols, ethers, esters, amines, phosphines, aromatics, carbon disul de, and hexamethylphosphoramide The effects of the third components vary considerably depending on the third component and the other two components of the initiator system Some additives increase stereoselectivity and/or activity, while others have the opposite effect Some increase stereoselectivity while decreasing activity or vice versa Some additives such as oxygen and water have deleterious effects on both activity and stereoselectivity Still other additives affect polymer molecular weight either exclusively or along with changes in initiator activity and stereoselectivity The high-mileage initiators achieve high activity by supporting (and nely dispersing) the transition metal component on MgCl2 .



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I converted Excel (.xls) to PDF (.pdf). But i used GemBox.Spreadsheet.dll & wnvhtmlconvert.dll. It may help you. Hide Expand Copy Code. using ...

B='\1/\(vz), e = '\1/\ (uz).

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High stereoselectivity is maintained and even increased by the Lewis base [Barbe et al, 1987; Chadwick, 2001; Chadwick et al, 2001; Chien and Hu, 1987; Chien and Bres, 1986; Chien et al, 1982; Galli et al, 1981; Pino and Mulhaupt, 1980; Soga et al, 1988, 1990] Various mechanisms have been proposed for the action of Lewis bases in improving stereoselectivity decreasing the reactivity of the less stereoselective sites (perhaps by altering the ligands) and increasing the number of stereoselective sites by assisting in their stabilization and/or dispersal in the support Both internal and external electron donors (Lewis bases) are used to produce the highmileage initiators An internal base is typically ball-milled with the support material and the transition metal component subsequently added with further mixing This is followed by the addition of a mixture of the group I III metal component with the external base.

(9.75) (9.76)

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Previous recipes used the same base, usually an aromatic ester such as diisobutyl phthalate, as both internal and external bases More recent recipes use an aromatic ester or diether as the internal base and an alkoxysilane, such as RR0 Si(OCH3 )2 or RSi(OCH3 )3 , as the external base The external base is needed, especially when an ester is used as the internal base, because the addition of the group I III metal component results in the loss of a large fraction of the internal base Without replacement of the lost base by the external base, there is a loss of stereoselectivity [Chadwick et al, 2001] An external base is seldom needed when a diether is used as the internal base The loss of diether during the initiator preparation is much less than the loss of the ester 8-4i 8-4i-1 Kinetics Observed Rate Behavior.

More specifically, we can choose </;' to satisfy (9.73) in the following way. Substituting (9.76) in (9.73) and expanding '\1/\ {'\1/\ (uz)}, we obtain

The kinetics of Ziegler Natta polymerization are complex. The relatively few polymerizations that are homogeneous behave in a manner generally similar to noncoordination ionic polymerizations (Chap. 5). The heterogeneous systems usually exhibit complicated behavior as shown in Fig. 8-15 [Boor, 1979; Bur eld, 1984; Bur eld et al., 1976; Cooper, 1976; Keii, 1972; Tait and Watkins, 1989]. The behavior described by plot 1 is usually observed when the particle size of the transition metal component is relatively large. The particles of the transition metal component consist of aggregates of smaller crystals. The mechanical pressure of the growing polymer chains cleaves these aggregates with the result that the initiator surface area, number of active sites, and polymerization rate increase with time. After this initial period, referred to as a buildup or settling period, a steady-state rate is reached, which

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