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on s -

Data from Chien and Hu [1987]. Units: (C*) % of Ti; [C*]I mol L 1 ; ks s 1 ; all other rate constants L mol 1 s 1 ; isotactic index percent of sample insoluble in re uxing n-heptane. c Values are for the isoselective sites.

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becomes favored by a factor of 25 The isotactic index increases from 682 to 960% when an external base is present together with the internal base The ktr;A , ktr;M , and ks values in Table 8-4 are those for the isoselective active sites These are lower than kpI by a factor of 104 106 , which results in high polymer molecular weights (M n 2:0 105 and 1:5 105 , respectively, with and without external base) Lower molecular weights are achieved only in the presence of H2 whose rate constant for transfer is much higher The aselective active sites yield lower molecular weights (M n 1:1 105 and 0:9 105 , respectively, with and without external base) than do the isoselective active sites The molecular weight distributions obtained with heterogeneous Ziegler Natta initiators vary considerably depending on the initiator.

over the cavity walls and the asymptotic condition lim v(r)





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X w =X n is slightly above 3 for the polymerization in Table 8-4, but most literature reports show values in the 5 30 range The broader distributions, found for the less isoselective polymerizations, are the result of initiators with multicenters The analysis of the system in Table 8-4 is based on a two-center model, but there are indications of the presence of more than two types of active centers for some initiators For example, resolution of the GPC molecular weight data in an ethylene polymerization by a titanium magnesium initiator system supported on silica indicated ve different molecular weight distributions, which were interpreted in terms of ve different active sites of different activities [Kissin, 2001a, 2003] Homogeneous Ziegler Natta polymerizations typically have narrower distributions than the heterogeneous systems since there is a narrower distribution of active sites of differing reactivities.

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The overall activation energies for the rates of most Ziegler Natta polymerizations fall in the range 20 70 kJ mol 1 ER is a composite of the activation energy for propagation and the heat of adsorption of monomer Although polymerization rates increase with temperature, reaction temperatures above 70 100 C seldom are employed High temperatures result in loss of stereoselectivity, a decrease in polymer molecular weight, as well as lowered polymerization rates due to the decreased stability of the initiator 8-4j Transition Metal Oxide Initiators.

The radiation condition implies that a linear combination of natural modes can only reproduce outgoing fields. Thus, it does not form a complete set capable of representing every conceivable quantum vacuum fluctuation which can also have incoming fields from infinity. To get a complete set of modes for the quantized radiation field, we must change the asymptotic boundary condition at infinity to allow for incoming and outgoing waves together, as in a scattering problem. The resulting modes will form a continuum. They are the modes ofthe universe, which were determined in Section 2.5.2 using precisely such a scattering formulation. There it was convenient to work with plane waves. Here, however, it is more convenient to formulate the asymptotic boundary condition in terms of spherical waves. So in place of Sommerfeld's radiation condition, we demand that [607] lim If>(r) = XI((}, '1')-r

Various supported transition metal oxides, such as CrO3 and MoO3 , initiate the polymerization of ethylene. The most active initiator is chromium oxide [Beach and Kissin, 1986; Pino et al., 1987; Ruddick and Badyal, 1998; Tait, 1989; Tait and Watkins, 1989; Thune et al., 2001; Witt, 1974]. Silica (SiO2 ) or aluminosilicates (mixed SiO2 /Al2 O3 ) are used as the support material. The support is sometimes modi ed with titania (TiO2 ). The CrO3 catalyst, referred to as a Phillips catalyst or initiator, is prepared by impregnating the nely divided support with an aqueous solution of CrO3 . The chromium loading is in the range 0.5 5 wt%, typically 1 wt%. The initiator is xed on the support surface by heating at 500 800 C and higher. This probably results in the reaction of surface hydroxyl groups in the support material with CrO3 to form chromate (XXV) and dichromate (XXVI) species.

8-51

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