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Sigwalt, 1976, 1979; Tsuruta, 1972] This is consistent with the mechanism for isoselective polymerization that attributes steric control to the initiator The initiator contains R and S enantiomeric polymerization sites in equal numbers such that R sites polymerize only R monomer and S sites polymerize only S monomer If the isoselectivity of R and S sites is less than complete, there is some cross-propagation of the two enantiomeric monomers and a decrease in the overall isotacticity of the reaction product As discussed in Sec 8-14a, an optically active polymer sample, composed of either all-R or all-S polymer molecules, can be synthesized by isoselective polymerization of a pure enantiomer, the pure R or pure S monomer, respectively The direction of optical rotation of the polymer is usually the same as the corresponding monomer Asymmetric enantiomer-differentiating polymerization occurs when one of the enantiomers polymerizes faster than the other.



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This type of process has also been referred to as stereoelection In the extreme case, one enantiomer (eg, the R monomer) is unreactive and polymerization of racemic monomer yields the optically active all-S polymer with the optically active R monomer left unreacted This does not occur unless the initiator is an (optically active) enantiomer itself An optically active Ziegler Natta initiator is obtained by using an optically active group I III metal compound in combination with the transition metal compound, such as Zn[(S)-2-methyl-1-butyl]2 plus TiCl4 The use of a chiral electron donor in a Ziegler Natta initiator has also been used to achieve asymmetric enantiomerdifferentiating polymerization [Carlini et al, 1977] Such polymerizations have also been studied with vinyl ethers, acrylates and methacrylates [Okamoto et al, 1979; Villiers, et al, 1978].

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For example, the S monomer is preferentially consumed in the polymerization of (R, S)-1,2-diphenylethyl methacrylate at 75 C in toluene using C2 H5 MgBr-( )-sparteine as the initiator [Okamoto et al, 1984] Asymmetric enantiomer-differentiating polymerization results from the presence of only one (either R or S) of two enantiomeric polymerization sites in the initiator a consequence of using a chiral initiator component One of the enantiomeric monomers is able to propagate at a faster rate The reactive monomer is usually the enantiomer having the same absolute con guration as the initiator in terms of the ordering of similar groups Similar groups are those having similar steric and polar effects This may not always correspond to both monomer and initiator having the same Cahn Ingold Prelog designation (Polymerizations in which the reactive enantiomer has the con guration opposite that of the initiator are known.

(}5 (}7

) Asymmetric enantiomer-differentiating polymerization is highly sensitive to the.

positions of chiral centers in both monomer and initiator [Carlini et al., 1974; Chiellini and Marchetti, 1973; Pino et al., 1967]. The maximum effect occurs when the chiral centers are as close as possible to the bonds (in both monomer and initiator) through which reaction takes place. Asymmetric enantiomer-differentiating polymerization is maximum for a monomer (e.g., 3-methyl-1-hexene) when the chiral center is in the a-position to the double bond, decreases sharply when the chiral carbon is in the b-position (e.g., 4-methyl-1-pentene), and essentially disappears when the chiral carbon is in the g-position (e.g., 5-methyl-1-heptene). Asymmetric enantiomer-differentiating polymerization seldom occurs if the chiral carbon in the initiator is in the g-position to the metal instead of in the b-position. If the polymerization sites are not prefectly isoselective, the result is a modi ed asymmetric enantiomer-differentiating polymerization behavior with some cross-propagation of the two enantiomeric monomers and a decrease in the overall isotacticity of the reaction product. The extent of asymmetric enantiomer-differentiating polymerization in an isoselective process is evaluated by measuring the optical activity of unreacted monomer a as a function of the extent of reaction p [Zhong et al., 2003]. The rates of reaction of R and S enantiomers are given by

(i6)1

d R kr C* R dt d S ks C* S dt 8-78 8-79

(i(})2 2!

where kr and ks are the rate constants for reaction of R and S enantiomers and [C*] is the concentration of polymerization sites. This treatment assumes that differentiation between R and S enantiomers is not dependent on whether the last monomer added to the propagating chain is R or S. Dividing Eq. 8-78 by Eq. 8-79 followed by integration yields

(i(})3 3!

R R 0 S S 0 r 8-80

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(i(})4 4!

where r kr =ks and the 0 subscripts indicate initial concentrations. The variables a and p are related to various concentration terms by

... }

a a0 S R S R S R S 0 R 0 8-81 8-82

(C.4)

p 1

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