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in which there is partial charge transfer between an electron donor and an electron acceptor. This type of polar effect is a general one often encountered in free-radical reactions [Huyser, 1970]. One usually observes the reactivity of an electron-donor radical to be greater with an electron-acceptor substrate than with an electron-donor substrate. The reverse is true of an electron-acceptor radical. The effect of polar effects on radical addition reactions will be considered in Sec. 6-3b-3.

1(112

3-6c-3

dV {V 1\ x*(r)} . {V 1\ x(r)} ,



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The use of the Mayo equation (Eq. 3-108 in its various forms) allows one to quantitiatively determine the effects of normal termination and transfer to monomer, initiator, and solvent on the molecular weight of the product and then adjust the reaction parameters to obtain the desired molecular weight. Two cases are encountered. Case 1 involves a reaction system that yields a molecular weight lower than needed. One analyzes the different terms on the right side of the Mayo equation to determine which one(s) is (are) responsible for the low molecular weight and the reaction parameters are then adjusted accordingly to increase the molecular weight. The initiation rate would be lowered if the low molecular weight is due to an excessively high initiation rate. If the initiator or

(A28)





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over 1,2-propagation is primarily a consequence of the lower steric hindrance at carbon 4 relative to carbon 2 for bonding to an incoming monomer molecule. The difference increases as the 2-position becomes substituted with the result that 1,4-polymerization is even more favored in the polymerizations of isoprene and chloroprene (Table 8-8). The stability of the polymer is probably also a factor, since the 1,4-polymer (a 1,2-disubstituted alkene) is generally more stable than the 1,2-polymer (a monosubstituted alkene). Several factors favor the preference of trans 1,4-polymerization over cis 1,4-polymerization. 1,3-Butadiene exists predominately in the transoid or s-trans conformation (ILa) as opposed to the cisoid or s-cis conformation (ILb). This is probably also the situation for

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isoprene [Craig et al., 1961; Hsu et al., 1969]. The conformation of the monomer need not translate into polymer stereochemistry since isomerization is possible after the s-trans or s-cis conformer adds to a propagating center. However, one expects predominance of the trans con guration of the allyl propagating radical (XLVIII) since the cis con guration involves steric hindrance to overlap among the p-orbitals of the carbon atoms of the allyl radical. Another factor is the greater stability of the trans 1,4-polymer over the cis 1,4-polymer. The con guration of the last monomer unit in the propagating chain is determined (with trans favored over cis) when the next monomer unit adds. The stereochemistry of the 1,3-diene units in copolymerization is expected to be the same as in homopolymerization of 1,3-dienes. This expectation has been veri ed in styrene-1,3butadiene copolymerizations at polymerization temperatures of 33 to 100 C [Binder, 1954]. 8-10b Anionic Polymerization

(V A X*) . (V A X) = V {X* A (V A X)} + X* . {V A (V A X)}

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The anionic polymerization of 1,3-dienes yields different polymer structures depending on whether the propagating center is free or coordinated to a counterion [Morton, 1983; Quirk, 2002; Senyek, 1987; Tate and Bethea, 1985; Van Beylen et al., 1988; Young et al., 1984] Table 8-9 shows typical data for 1,3-butadiene and isoprene polymerizations. Polymerization of 1,3-butadiene in polar solvents, proceeding via the free anion and/or solvent-separated ion pair, favors 1,2-polymerization over 1,4-polymerization. The anionic center at carbon 2 is not extensively delocalized onto carbon 4 since the double bond is not a strong electron acceptor. The same trend is seen for isoprene, except that 3,4-polymerization occurs instead of 1,2polymerization. The 3,4-double bond is sterically more accessible and has a lower electron density relative to the 1,2-double bond. Polymerization in nonpolar solvents takes place with an increased tendency toward 1,4-polymerization. The effect is most pronounced with

(A.29)

TABLE 8-9 Effect of Solvent and Counterion on Stereochemistry in Anionic Polymerization of 1,3-Dienesa Structure of Polymer (%) Cis 1,4 Trans 1,4 3,4 1,2

in (A.28) we can transform the volume integral of the first term on the right-hand side of (A.29) into a surface integral using Gauss's theorem: (A. 30)

1,3-Butadiene (at 0 C)

Thus,

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