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) Isoselective initiators of the traditional Ziegler Natta type are heterogeneous, with chirality attributable to the chiral crystal lattice in the vicinity of the initiator active center The chirality of the homogeneous metallocene initiators resides in their molecular structures; thus, the initiator molecule is chiral Some chiral initiators have structures such that alternate monomer placements occur with opposite faces of the monomer to yield the syndiotactic polymer This is syndioselective polymerization proceeding with catalyst site control and is usually observed only with some homogeneous initiators, both traditional Ziegler Natta and metallocene When the initiator is achiral, the active sites can coordinate equally well (more or less) with either face of the incoming monomer This generally results in either atactic or syndiotactic polymers depending on the speci c interaction of the initiator fragment G, polymer chain end, and incoming monomer as well as the reaction temperature.

J (z*)r(l - z*)r-ldz*,

Syndioselective polymerization occurs in systems where coordination accentuates the repulsive interactions between substituents on the polymer chain end and incoming monomer The driving force for syndiotactic placement is similar to that previously described for low-temperature polymerizations with free propagating centers, but the initiator exaggerates the situation Instead of obtaining a polymer with moderate syndiotacticity, say, 60% syndiotactic polymer, one may obtain 80% or 90% or higher syndiotacticity The syndiotacticity increases with decreasing polymerization temperature The exact nature of the initiator needed for isoselective polymerization differs depending on the monomer The ease of imposing catalyst site control on the entry of a monomer unit into the polymer chain increases with the ability of the monomer to coordinate with initiator and this depends on monomer polarity Monomers, such as (meth)acrylates and vinyl ethers, with polar functional groups take a strong role in the coordination process.

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Ethylene, a-ole ns, and other alkenes without polar functional groups have poorer coordinating power The result is that nonpolar monomers require the use of initiators with very strong coordinating power for isoselective polymerization For the traditional Ziegler Natta initiators, this requires heterogeneous initiators to impose the most severe restriction on entry of a monomer into the propagating chain Soluble traditional Ziegler Natta initiators can yield only atactic and syndiotactic polymers Heterogeneity is not required for isoselective polymerization with the metallocene initiators The required level of coordination can be achieved through the appropriate structure of the metallocene..

6

For polar monomers, heterogeneity is seldom a requirement for isoselective polymerization with traditional Ziegler Natta initiators; syndiotactic polymers are obtained only with the soluble initiators. Styrene and 1,3-dienes are intermediate in behavior between the polar and nonpolar monomer. These monomers undergo isoselective polymerization with both homogeneous and heterogeneous traditional Ziegler Natta initiators.

assuming the one of Q encoding, then e will give the functional form of a p that will produce consistent estimators of the posterior probability of class membership. For T = 1, the sum of squares penalty function is recovered, while for T = 0 crossentropy is recovered. In the case of targets other than (0, I}, for example {0.1, 0.9) targets, the outputs will not be the posterior probabilities (Pao, 1989). Consider a two class problem, C1 and Cz, with target values and b respectively. Then

8-4 TRADITIONAL ZIEGLER NATTA POLYMERIZATION OF NONPOLAR ALKENE MONOMERS Since the original discoveries of Ziegler and Natta, there have been many hundreds of different combinations of transition and group 1 III metal components, often together with an added electron donor, studied for use in alkene polymerizations. The resulting initiators exhibit a range of behaviors in terms of activity (reactivity) and stereoselectivity. Activity is often expressed as kg polymer formed per gram (or mole) of transition metal (or transition metal compound). Sometimes it is given as the activity per hour and sometimes it is given as the activity per polymerization run. The term productivity is often used as a synonym for activity. Modi cation of an initiator system to increase activity has often come at the expense of stereoselectivity. The great utility of the Ziegler Natta initiator system is the ability to change one or another of the components, or to add additional components (usually electron donors) to achieve very high stereoselectivity with high activity. The choice of the initiator components evolved in an empirical manner because of a less-than-complete understanding of the detailed structure of these initiators and the mechanism of their stereoselectivity. 8-4a Historical Development of Ziegler Natta Initiators

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