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produced by radical polymerization; see Sec 8-11) Natta used Ziegler s initiators to achieve stereoselective polymerizations (both isoselective and syndioselective) of propene and other 1-alkenes (a-ole ns) [Natta, 1965] This was a huge achievement since a-ole ns cannot be polymerized to high-molecular-weight polymer by radical or other ionic initiators (Secs 3-7c, 5-2b) The scienti c and practical signi cance of their work earned Natta and Ziegler the joint award of the 1963 Nobel Prize in Chemistry [Mulhaupt, 2003] The work of Ziegler and Natta led to the development of a very large number of twocomponent initiator systems consisting of an organometallic compound or hydride of a group I III metal together with a halide or other derivative of a group IV VIII transition metal [Pasquon et al, 1989] The polymerizations are generally carried out in a hydrocarbon solvent such as n-hexane.

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The more important component of the initiator system is the transition metal compound The function of the group I III metal compound is to modify and activate the transition metal compound for initiation Some of the compounds used as the group I III metal component are triethylaluminum, diethylaluminum chloride, and diethylzinc; titanium trichloride or tetrachloride, vanadium trichloride, and chromium triacetylacetonate are examples of the transition metal component [Choi and Ray, 1985; Corradini et al, 1989; Pino et al, 1987; Tait, 1989] These initiator systems are the traditional Ziegler Natta initiators The actual initiator species have not been isolated, and their structures are not well understood One mixes the two components, perhaps adds some other compounds for enchancements in reactivity and/or stereoselectivity, and then adds the mixture (which usually is heterogeneous) to the monomer the result is enormously useful stereoselective polymerizations.

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These were still the initiators used in more than 95% of commercial processes in 2002 Since the mid-1980s there has been another revolution the discovery and development of metallocene initiators within the Ziegler Natta revolution Bis(cyclopentadienyl)titanium dichloride and bis(indenyl)zirconium dichloride are examples of simple metallocene initiators More complex metallocenes have substituents on the organic ligands and the ligands are joined together through 2 CH2 and other bridges The metallocene initia CH tors, unlike the traditional Ziegler Natta initiators, are molecules that can be isolated, analyzed by techniques such as NMR, and puri ed Metallocene initiators are also homogeneous in the reaction systems They offer the potential for tailor-making initiators to perform highly stereoselective polymerizations of speci c monomers Utilization of the metallocene initiators requires the addition of a group I III metal compound, as in the case of the traditional Ziegler Natta initiators Some clari cation is needed regarding terminology.

The metallocene initiators are a type of Ziegler Natta initiator, derived from a combination of a transition and group I III metal compounds However, the growing importance of metallocenes leads us to distinguish them from the traditional Ziegler Natta initiators by using the term metallocene All of these initiators can be considered as coordination initiators, initiators that perform stereoselectively due to coordination This term includes initiators other than the Ziegler Natta and metallocene initiators; examples are n-butyllithium, phenylmagnesium bromide, and boron tri uoride Polymerizations brought about by coordination initiators are referred to as coordination polymerizations The terms isoselective and syndioselective are used to describe initiators and polymerizations that produce isotactic and syndiotactic polymers, respectively 8-3b-2 Mechanism of Stereoselective Placement.

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Coordination initiators perform two functions. First, they supply the species that initiates the polymerization. Second, the fragment of the initiator aside from the initiating portion has unique coordinating powers. Coordination of this fragment (which may be considered as

Hence p is minimized when the network outputs are equal to the posterior probability of class membership . T h a t the MLP directly estimates the a posteriori probability P(C,JX)when the targets are one of Q and an appropriate objective function is used, has appeared a number of times in the literature. Richard and Lippmann (1991) point out that it is true for the sum of squares and cross-entropy penalty functions. Hampshire and Perlmutter (1990) consider the general conditions on p under which the network outputs may be interpreted as probabilities. They show that if a function e satisfies e ( z * )=

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