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etc:; etc:



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= 211"3

where kp is the rate constant for propagation. Propagation with growth of the chain to highpolymer proportions takes place very rapidly. The value of kp for most monomers is in the range 102 104 L mol 1 s 1 . This is a large rate constant much larger than those usually encountered in step polymerizations (see Table 2-8). At some point, the propagating polymer chain stops growing and terminates. Termination with the annihilation of the radical centers occurs by bimolecular reaction between radicals. Two radicals react with each other by combination (coupling) or, more rarely, by

(3.71)

disproportionation, in which a hydrogen radical that is beta to one radical center is transferred to another radical center. This results in the formation of two polymer molecules





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As d3k/ Jk2 + J.L2 is an invariant quantity,3o and f d3r (FtF+ + J.L2 A~A+) is a four-vector, it follows that (l1..~l1..+ + J.L2~~~+)/Jk2 + J.L2 is a four-vector. This shows a way of defining densities of probability and of probability current that form a four-vector3 1: Instead of insisting on a wavefunction composed of F and A, we should take as our wavefunction (3.67) and (3.69) with E+ and A+ replaced by E+/ \!k 2 + J.L2 and A+/ \!k 2 + J.L2, respectively. So we define the wavefunction components as

one saturated and one unsaturated:

w (R) =

Termination can also occur by a combination of coupling and disproportionation. The two different modes of termination can be represented in general terms by

4 (I() '"

where ktc and ktd are the rate constants for termination by coupling and disproportionation, respectively. One can also express the termination step by

d3 k e ik. r E",(k, t) \!k 2 +J.L2'

3-18

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kt aktc 1 a ktd 3-19

(3.72)

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where a and (1 a) are the fractions of termination by coupling and disproportionation, respectively. The term dead polymer signi es the cessation of growth for the propagating radical. The propagation reaction would proceed inde nitely until all the monomer in a reaction system were exhausted if it were not for the strong tendency toward termination. Typical termination rate constants are in the range of 106 108 L mol 1 s 1 or orders of magnitude greater than the propagation rate constants. The much greater value of kt (whether ktc or ktd ) compared to kp does not prevent propagation because the radical species are present in very low concentrations and because the polymerization rate is dependent on only the one-half power of kt (as will be discussed in Sec. 3-4a-2). (Polymerizations with little or no termination occur under special conditions Sec. 3-15). 3-3b Rate Expression

d 3 k e ik . r Aa(k, t)

Equations 3-13 through 3-19 constitute the detailed mechanism of a free-radical-initiated chain polymerization. The chain nature of the process resides in the propagation step (Eq. 3-15) in which large numbers of monomer molecules are converted to polymer for each initiating radical produced in the rst step (Eq. 3-14). In order to obtain a kinetic expression for the rate of polymerization, it is necessary to assume that kp and kt are independent of the size of the radical. This assumption is inherent in the notation used in Eqs. 3-15 through 3-18. It is exactly the same assumption the equal-reactivity assumption that was employed in deriving the kinetics of step polymerization. Very small radicals are more reactive than propagating radicals, but this effect is not important because the effect of size vanishes at the dimer or trimer size [Gridnev and Ittel, 1996; Kerr, 1973]. There are limitations to the equal-reactivity assumption with respect to the sizes of propagating radicals, and this is discussed in Secs. 3-10 and 3-11b.

\!k 2 + J.L2'

3-180

(3.73)

3-181

where Q stands for the sign of the frequency. We now have a four-vector candidate to be our probability four-current density: wtw + J.L 24 t4 Moreover, from (3.57) and (3.58), we see that wand 4 satisfy the same equations as F and A; that is,

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