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R1, R1, R1 GetFileSize R0, PE_header R0, R1, R2, R3, send victims_socket =PE_header =4 R3, R3 ; send filesize

ln ! pe p 2pe 1 1 1 M 0 t 2k1 pe p pe 2-68

Equation 2-68 can be used to calculate the extent of conversion at any time if k1 and pe are known. pe is experimentally determined, or calculated from Eq. 2-61 if K is known. From experimental values of p as a function of time, Eq. 2-68 yields a straight line when the left side of the equation is plotted against time. The slope of the line then allows one to calculate k1 .

m m m m r (mr) = 2 (rr)

+ ......

(mmmr) = (mmrm)

(mr) = 2 (mm) (rrrm) = (mmrr) = 2 (rmmr)

_send_next_file_part ldr ldr ldr ldr eor str bl ldr tst beq ldr ldr eor bl b _get_EOF ldr bl R0, hFile R1, =PE_header R2, =PE_header_size R3, =fd_set R4, R4, R4 R4, [SP] ReadFile ; read part of file R2, fd_set R2, R2 _get_EOF

Only mr (rrrm) = (rrmr)

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amount of steric bulk required at the active site in order to observe high enantioselectivity between the two monomer faces. The monomer and various transition metal ligands contribute to the steric bulk at the active site. For propene polymerization, the enantioselectivity in the rst monomer unit added is low for R methyl, appreciable for R ethyl, and very high for R isobutyl or phenyl. Enantioselectivity of the rst addition is enhanced for larger-sized monomers such as styrene and vinylcyclohexane compared to propene and for larger-sized halogen ligands. The various steric effects act in a cooperative manner. Thus, addition of the rst monomer unit for propene polymerization is as isoselective as all subsequent monomer units when TiI3 is used instead of TiCl3 . The Cossee Arlman mechanism as originally proposed has a weakness the back- ip is required to explain isoselective placement since the two active (coordination) sites are assumed to be enantiotopic. However, the structure of the traditional Ziegler Natta heterogeneous initiators is not suf cently understood to either support or reject the assumption of enantiotopic sites. Further, even if the sites are enantiotopic, there is no overwhelming reason why the polymer chain is more stable at one site than the other which is the rationale for the back- ip. The mechanism of isoselectivity with various metallocene initiators is much better understood since these are initiators whose molecular structures are well-established [Busico and Cipullo, 2001; Busico et al., 1997, 1999; Cavallo et al., 1998; Ewen, 1999; Rappe et al., 2000; Resconi et al., 2000]. Considerable advancements in understanding heterogeneous Ziegler Natta initiators occur if one assumes that the active sites in these initiators mimic those in metallocene initiators. Two types of metallocene initiators offer possible models

.. . .

for the isoselective active sites in heterogeneous Ziegler Natta initiators, the C1 - and C2 symmetric metallocenes. These will be discussed in greater detail in Secs. 8-5a-2 and 8-5a-4. The following gives a brief overview with speci c application to the heterogeneous Ziegler Natta initiators: 1. C1 -symmetric initiators have a pair of diastereotopic (nonequivalent) sites; one site is sterically crowded and enantioselective, and the other site is less crowded and nonselective. The propagating polymer chain always prefers the less crowded site, but monomer coordination and migratory insertion occur at the more crowded enantioselective site. The polymer chain then back- ips to the less crowded site. This model offers a rationale for the back- ip of the polymer chain the polymer chain is less stable at the more crowded site. 2. C2 -symetric initiators have a pair of equivalent homotopic sites, both of which prefer the same monomer enantioface, that is, both sites prefer the re enantioface or both prefer the si face. Isoselective propagation proceeds with or without migratory insertion since coordination and insertion of monomer at either site give the same stereochemical result.

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