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highly solvated ion pairs, the transition state XXIII involves greater charge delocalization than does the initial state. Polar solvents stabilize the initial state more than the transition

dv {(31(W, v)B(v) + (32(W, v)Bt(v)},

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7-47

(7.145)



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state. This is the typical behavior for reaction between a charged substrate and neutral nucleophile or between a neutral substrate and charged nucleophile in SN2 reactions. It was indicated earlier that the covalent species detected in many systems by NMR and other methods may be dormant, not active (propagating), species. However, propagation rate constants can be calculated on the assumption that covalent species are active. This has been done in a number of systems, such as in polymerizations of THF by very strong acids and their esters (CF3 SO3 H, C2 H5 OSO2 CF3 ) in low-polarity solvents such as CCl4 and CH2 Cl2 . The rate constant for covalent propagation is about 102 103 lower than the rate constant for the corresponding ionic species [Kobayashi et al., 1975; Matyjaszewski, 1986; Penczek and Kubisa, 1989a,b]. Even if one assumes covalent propagation, the reactivity of covalent species is so much lower than the reactivity of ionic species that more than 95% of the total polymerization rate is carried by the ionic propagating species. 7-2b-5-c Degree of Polymerization. The quantitative dependence of the degree of polymerization on various reaction parameters has been described [Hirota and Fukuda, 1987; Tobolsky, 1957, 1958; Tobolsky and Eisenberg, 1959, 1960] for an equilibrium polymerization involving initiation





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defined such that they diagonalize the Hamiltonian (7.144), that is,

7-48

[C(w), ill = hwC(w),

Xn M 0 M c I 0 I c 7-49

where M c and I c are the unreacted monomer and initiator concentrations at equilibrium. The polymer molecular weight increases with decreasing I 0 and increasing M 0 . Larger values of Kp , the equilibrium constant for Eq. 7-41, and smaller values of Ki yield higher polymer molecular weights by decreasing M c and increasing M c , respectively. 7-2b-6 Energetic Characteristics

(7.146)

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7-2b-6-a Effect of Temperature on Rate and Degree of Polymerization. The effects of temperature on the rate and degree of polymerization of cyclic ethers and acetals vary considerably depending on the speci c reaction system. Variations due to different monomers, solvents, initiators, and coinitiators are generally analogous to those observed in ionic polymerizations of alkenes (Secs. 5-2f, 5-3d-2). Increased temperature almost always results in an increase in the rate of polymerization; that is, ERp is positive. Few ERp or individual activation energies for initiation, propagation, and termination transfer are available. Typical values of ERp or Ep are in the range 20 80 kJ mol 1 with most values in the upper part of that

and are annihilation operators, with their Hermitian conjugates being creation operators, satisfying the usual commutation relations,

TABLE 7-2 Effect of Temperature on Polymerization of Oxetanea Temperature ( C) 80 0 50 100

[C{w),

To determine what fields you need in your database, do a little planning. Decide what kinds of information you want to track in your database and what sorts of reports and queries you want to generate to view your data. For best results, use the suggested fields; you can always remove fields that you do not use at a later time. (For help removing fields from a table, see the section Delete a Field from a Table later in this chapter.)

Intrinsic Viscosity of Polymer (dL g 1 ) 2.9 2.1 1.3 1.1

ct (w')] = 8{w -

Ultimate Conversion of Monomer (%) 95 94 64 62

(7.147) (7.148)

Proportion of Tetramer (%) 4 10 66 62

As in the matter case, the reader can easily check later that (7.148) is satisfied automatically and does not have to be imposed to derive the solution. We must now determine al{w), a2{w), f31{W,V), and f32{W,V) using (7.144), (7.145), (7.146), (7.147), and (7.148). From (7.144), (7.145), and (7.148), we obtain

Data from Rose [1956].

Wcal{W)

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