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3 The effect of the bridge between ligands differs depending on the ligands For the unsubstituted indenyl ligand, isoselectivity and molecular weight increase in the order CH2 < CH2 CH2 < (CH3 )2 C < Si(CH3 )2 However, for the 3-t-butylindenyl ligand, CH2 and (CH3 )2 C are highly isoselective, and more so than CH2 CH2 and Si(CH3 )2 The bite angle and stereorigidity of the system are affected differently by the bridge depending on the ligands Initiators with bridges longer than two atoms are not useful Markedly decreased isoselectivity and activity is observed with the CH2 CH2 CH2 bridge Bulkier or longer bridges such as (CH3 )2 SiCH2 CH2 Si(CH3 )2 and (CH3 )2 SiOSi(CH3 )2 yield initiators inactive for propene polymerization Various other types of bridges have been studied with poor results.



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where k n == n1r/ L, '"Y == -In Irl/2L, kn == k n - A, and A == [arg(r) - 1rl!2L. To sum the series Sand S', use the series summation result (see Chap. XII, Sec. 125, p. 370 of [77])





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This includes bridges through the 6-membered rings in Ind and H4 Ind systems and two bridges in Cp systems 4 The introduction of heteroatoms into the ligands via alkoxy and trisubstituted amino groups has been explored to improve initiator performance through electronic effects This approach is not promising as initiator performance deteriorates with very few exceptions The exceptions do not result in performance enhancements; at best, performance is unaffected 5 Bis uorenyl zirconocenes generally are neither highly active nor highly isoselective 6 Polymerizations are highly regioselective with regioirregular placement generally in the range 03 10%, but regioselectivity is very sensititive to the ligands At the extremes, there is less than 0002% regioerrors with rac-CH2 (3-t-Bu-Ind)2 ZrCl2 /MAO, but 20% with rac-CH2 CH2 (2,4-Me2 -H4 Ind)2 ZrCl2 /MAO C2 metallocenes generally are less regioselective than the metallocenes that are syndioselective or aselective.

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Table relationships enable you to combine related information for analysis. For example, you might define a relationship between a table containing customer contact information and a table containing customer orders. With that table relationship defined, you could perform a query, for example, to locate all customers who have ordered the same product. To define table relationships, click the Database Tools tab

But be careful that it is valid only on the window 0 < x < 2L, as the series above is discontinuous at the boundaries of this window. To avoid the discontinuities and remain within the window, you can adopt a sort of regularization procedure writing Sas

Some 3,1-placements (CH2 CH2 CH2 ) are observed in propene polymerization, a result of isomerization after a 2,1-placement [Busico and Cipullo, 2001] 8-5c-2 Effect of Reaction Variables.

Remembering that sin([kn - knl]L)/(kn - knl)

Polymerization at higher temperature increases the reaction rate but decreases isoselectivity, regioselectivity, and polymer molecular weight. For example, (mmmm) decreases from 0.92 to 0.83 for polymerization of liquid propene with rac-C2 H4 (Ind)2 ZrCl2 /MAO when the temperature is increased from 20 to 70 C. M v decreases from 56,000 to 19,600, and the regioirregular fraction increases from 0.4 to 0.7%. Similar effects were observed in the polymerization of 1-hexene by Me2 Si(H4 Ind)2 ZrCl2 /MAO [Zhao et al., 2000]. Increased temperature affects the polymerization by decreasing the rigidity of the initiator and propagating species (increased uxionality). The result is epimerization of the propagating chain end, speci cally, scrambling the chirality of the last monomer unit inserted into the propagating chain (the rst monomer unit attached to the transition metal atom). The greater the inherent stereorigidity of the initiator, the less the effect of increased temperature on polymerization. Isoselectivity decreases with decreasing monomer concentration. Epimerization of the propagating chain end is a unimolecular process, unaffected by monomer concentration. propagation is slowed by decreased monomer concentration, allowing time for epimerization to occur. The effect varies considerably depending on the initiator. For rac-C2 H4 (Ind)2 ZrCl2 / MAO, (mmmm) decreases from 0.87 to 0.55 when the monomer concentration is decreased from 11 to 0.4 mol L 1 . The same effect is observed in the polymerization of 1-hexene by Me2 Si(H4 Ind)2 ZrCl2 /MAO [Zhao et al., 2000]. In the extreme case of very high dilution, the polymer molecular weight decreases enormously and the polymer becomes atactic. The polymerization is less sensitive to monomer concentration for the more stereorigid rac-Me2 Si

The production of linear polymers by the step polymerization of polyfunctional monomers is sometimes complicated by the competitive occurrence of cyclization reactions. Ring formation is a possibility in the polymerizations of both the A and A plus B types. B A B

+ 6. - iT] L) }

Reactants of the A type such as amino or hydroxy acids may undergo intramolecular B cyclization instead of linear polymerization

9.6 Using the canonical commutation relations for the radiation field inside the cavity,19

2-69 2-70

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