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Data from Def eux et al. [1983]. Calculated from E values of solvent and monomer assuming additivity of volumes and E of mixture to vary with volume fraction of solvent.

R(k)



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solutions of isobutylene in solvents (eg, CH2 Cl2 , CH3 Cl) more polar than isobutylene [Kennedy et al, 1977] Ionic propagating species (either free ions or ion pairs) are not suf ciently stable and do not form unless the reaction medium possesses some minimum solvating ability The preceding discussion assumes that the effect of solvent polarity on reaction rate (and polymer molecular weight) manifests itself only by altering the concentration of propagating centers However, solvent polarity is also expected to alter propagation rate constants, kp and kp One expects kp to decrease with increasing solvent polarity [Ledwith and Sherrington, 1974] The transition state for propagation by a free ion involves charge dispersal, so that solvents of higher polarity stabilize the reactants more than the transition state [Reichardt, 1988] The effect of solvent polarity on kp is more dif cult to predict.

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Whether increased solvent polarity increases or decreases kp depends on whether the transition state has a higher or lower dipole moment than the ion pair There are very few data available on the effect of solvents on the different propagation rate constants A comparison of reported kp values for styrene, ethyl vinyl ether, and isopropyl vinyl ether in different solvents shows the expected decrease in propagation rate constant with increasing solvent polarity [Def eux et al, 1983; Sawamoto an Higashimura, 1978, 1979] Table 5-8 shows data for isopropyl vinyl ether in radiation polymerization at 30 C A plot of ln kp versus 1=E is reasonably linear with a positive slope as expected for the reaction of an ion and neutral molecule [Reich erdt, 1988].

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Data for kp as a function of solvent polarity are available for the polymerization of styrene by 1-chloro-1-(4-methylphenyl) ethane/TiCl4 at 80 C in methylcyclohexane methyl chloride [De et al, 2003] kp increased by a factor of $3 when the solvent polarity was increased from 20% methyl chloride to 60% methyl chloride This effect indicates that the transition state has a higher dipole moment than do the reactants, a consequence of increased charge separation in the ion pair The need for solvation of ionic propagating species in cationic polymerization is evident when reaction is carried out in media of low dielectric constant In addition to lowered polymerization rates in poorly solvating media, one frequently encounters increased kinetic orders in one of the reactants The polymerization rate may show an increased order of dependence on the monomer, initiator, or coinitiator.

b(k)

Thus, the rate for the tin (IV) chloride polymerization of styrene depends on [M]2 in benzene solution and [M]3 in carbon tetrachloride solution [Okamura and Higashimura, 1956a,b, 1960] Carbon tetrachloride is a poor solvating agent compared to benzene, and the higher order in styrene concentration is due to styrene taking part in solvation of propagating species At high concentrations of styrene (and also in neat styrene) the order in styrene decreases to 2 as the reaction medium becomes equivalent to the benzene system (That benzene is a better solvating medium than.

27rt:~~(k)

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carbon tetrachloride is not entirely clear from a consideration of dielectric constants since the values are quite close 228 and 224 for benzene and carbon tetrachloride, respectively N However, other measures of solvating power such as the ET scale show the difference N between benzene and CCl4 The ET value for a solvent is derived from the energy of UV excitation for a pyridinium N-phenoxide betaine dye in the solvent Benzene and CCl4 N have ET values of 0111 and 0052, respectively, with larger values being indicative of higher solvating power [Reichardt, 1988]) The polymerization of styrene by trichloroacetic acid without solvent and in 1,2-dichloroethane and nitroethane solutions illustrates the situation where the initiator solvates ionic propagating species [Brown and Mathieson, 1958].

dk't:vac(k')

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