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, 2001; Li et al, 1997; Nguyen et al, 2000; Shiono et al, 1998; Soga et al, 1994; Yasuda, 2001; Yasuda et al, 1993] Metallocenes based on both groups 3 and 4 transition metals initiate polymerization, although the group 3 metallocenes (Sc, Y, La) are somewhat more active than the group 4 metallocenes Table 8-13 shows various initiators and their stereoselectivity in MMA polymerization Studies on initiators other than the metallocenes have recently begun the last entry in Table 8-13 is for an ansa-cyclopentadienyl amido initiator High stereoselectivity, both isoselective and syndioselective, are observed depending on the initiator The level of stereoselectivity is somewhat less than that observed with a-ole ns, but this may be due only to the much smaller effort expended to date for MMA Propagation proceeds through an enolate species in the bimetallic mechanism described by Eq.



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(B.2)

8-73 in which two metallocene species are involved one is a neutral enolate, and the other is the corresponding metallocenium cation [Collins et al, 1994; Li et al, 1997] In LV, the propagating chain is coordinated at the neutral transition metal center (Zra ) and monomer.

(B.3)

at the transition metal cation center (Zbb ). Monomer insertion into the polymer chain proceeds with the electron ow indicated by the arrow in LV. The result is LVI with an empty coordination site, ready to coordinate the next monomer unit and facilitate subsequent





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Now inside a perfect conductor there can be no electric field, then (B.3) reduces to (A.5). To obtain the boundary condition for the magnetic field (A.6), we integrate (2.43) over the volume of the cylinder. Using the Gauss integral theorem, taking 8h -+ 0 we obtain n Bis - n Blinside = O. (B.4) Now we are only interested in dynamic fields here, and from (2.44) we see that as the electric field vanishes inside the wall, the dynamic magnetic field must vanish as well. Then (B.4) implies that the boundary condition for the magnetic field is that its component normal to the wall must vanish [i.e., (A.6)].

8-73

1 2 3

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monomer insertion The roles of the neutral and cationic metallocenes alternate with each monomer insertion The rationale for the bimetallic mechanism, instead of a monometallic mechanism, is that a group 4 transition metal may not be suf ciently electropositive for one metal center to coordinate with two different oxygens (one from the enolate species and one from monomer) A monometallic mechanism is assumed for MMA polymerization with group 3 metallocenes since the group 3 metals are larger and more electropositive than group 4 transition metals [Boffa and Novak, 2000] Metallocene polymerization of MMA proceeds with differences compared to polymerizations of ethylene and a-ole ns A moderately coordinating anion such as [B(C6 H5 )4 ] can be used with MMA because the polar MMA can displace it from the initiator s coordination site Alkene monomers are generally unable to displace [B(C6 H5 )4 ] and polymerization does not proceed.

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The polarity of MMA and, more speci cally, its Lewis base character prevents polymerization if the monomer and coinitiator are mixed together prior to the addition of monomer [Cameron et al, 2000] Monomer coordinates strongly to the coinitiator and renders the coinitiator ineffective for reaction with the metallocene Polymerization is accomplished by mixing the metallocene and coinitiator together to form the active initiating species prior to the addition of monomer Another approach involves the addition of a large excess of another Lewis acid such as diethylzinc to displace the coinitiator from monomer prior to addition of initiator There is a strong interest in copolymerization of alkenes with polar monomers to alter the characteristics of a nonpolar polymer such as polyethylene or polypropene by introduction of polar functional groups The polar groups would allow control over properties such as adhesion, compatibility with other polymers, solvent resistance, and rheological behavior.

THE TETRACTYS, Or high Matheis, with her chann severe Of line and number, was our theme; and we Sought to behold her unborn progeny, And thrones reserved in Truth's celestial sphere: While views, before attained, became more clear; And how the One of Time, of Space the Three, Might, in a chain Symbol, girdled be: And when my eager and reverted ear Caught some faint echoes of an ancient strain, Some shadowy outlines of old thoughts sublime, Gently he smiled to see, revived again, In a later age, and occidental clime, A dimly traced Pythagorean lore. A westward floating. mystic dream of FOUR. -William Rowan Hamilton [327]

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