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that the square of its diameter is 1/4.

Data from Williams and Taylor [1969]. Data from Williams et al. [1967]. c Data from Sauvet et al. [1986]. d Data from Rooney [1976, 1978]. e Data from Subira et al. [1988], Def eux et al. [1983]. f Data from Williams et al. [1976]. g kp 4:1 104 L mol 1 s 1 . h kp 5:0 104 L mol 1 s 1 .

t:vac(kn,) (an, - a~,) sin ([x + L]kn') '



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by ionizing radiation or trityl salts Values of kp for two of the reaction systems are also included A comparison of the kp and kp values for the styrene, p-methoxystyrene, and N-vinylcarbazole polymerizations shows the free-ion propagation rate to be an order of magnitude higher than the ion-pair propagation rate constant Although there are relatively few other systems in which reasonably accurate measures of both kp and kp are available, it is generally considered that the reactivity of free ions is no more than a factor of 5 20 greater than the reactivity of ion pairs in cationic polymerization [Gandini and Cheradame, 1985; Matyjaszewski, 1989; Mayr, 1990; Mayr et al, 1988; Sauvet and Sigwalt, 1989] The counterion is typically quite large for cationic polymerization (eg.

(9.24)





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, SbCl , CF3 SO ); 6 3 the ion pair is a very loose ion pair with little difference in availability of the positive charge center for reaction compared to the free ion A comparison of Table 5-1 through 5-3 with corresponding data for radical chain polymerization (see Table 3-10 and 3-11) allows us to understand why cationic polymerizations are generally faster than radical polymerizations The propagation rate constants in cationic polymerization are similar to or greater than those for radical polymerization However, the termination rate constants are considerably lower in cationic polymerization The polymerization rate is determind by the ratio of rate constants kp =kt in cationic polymerization and 1=2 kp =kt in radical polymerization The former ratio is larger than the latter by up to 4 orders of magnitude depending on the monomers being compared.

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Cationic polymerization is further favored, since the concentration of propagating species is usually much higher than in a radical polymerization The concentration of propagating species is typically 10 7 10 9 M, much lower than that in cationic polymerization Table 5-3 shows the order of reactivity of monomers in propagation It is not a simple matter to explain the order of propagation rate constants for a set of monomers because there are variables the reactivity of the monomer and the reactivity of the carbocation For example, carbocation stability is apparently the more important feature for isopropyl vinyl ether and results in decreasing its propagation reactivity compared to isobutylene..

9This dielectric-delta-function mirror was introduced in (573) and subsequently adopted in other works, including [43, 3911. 10 As this is only it shift of the resonances, one could in principle still use (9.1) if, instead of the usual perfect cavity modes, one uses perfect cavity modes with the resonances shifted by the appropriate amount first order in the transmissivity.

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TABLE 5-4 Monomer Transfer Constant for Styrene Initiator SnCl4 SnCl4 SnCl4 TiCl4 TiCl4 TiCl4 TiCl4 FeCl3 BF3 BF3 CF3 SO3 H

an" However, as a definition of an', it is incomplete. It defines only the "imaginary" quadrature of an" As we are free, then, to define the "real" quadrature of an', let us define it in such a way that the internal magnetic field can also be described by an expression formally similar to its perfect cavity expression. We are allowed to do so because the perfect cavity modes for the magnetic field also form a complete set for the space inside the cavity. So we write the magnetic field as

Solvent fH CCl4 -fNO2 (3 : 7) C2 H5 Br fH (CH2 Cl)2 -fH (3 : 7) CH2 Cl2 CH2 Cl2 fH fH CH2 Cl2 CH2 Cl2

Bin(X)

Temperature ( C) 30 0 63 30 30 60 90 30 30 50 20

t:vac(kn,) (an'

Data from Okamura and Higashimura [1956a,b, 1960]. Data from Endres and Overberger [1955]. c Data from Biddulph and Plesch [1960]. d Data from Sakurda et al. [1958]. e Data from Mathieson [1963]. f Data from Kennedy and Feinberg [1978], Kennedy et al. [1977]. g Data from Kunitake and Takarabe [1979].

+ a~,) cos ([x + L]kn') '

5-2e-4

(9.25)

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