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The steady-state assumption is not unique to polymerization kinetics. It is often used in developing the kinetics of many small-molecule reactions that involve highly reactive intermediates present at very low concentrations conditions that are present in radical chain polymerizations. The theoretical validity of the steady-state assumption has been discussed [Kondratiev, 1969] and its experimental validity shown in many polymerizations. Typical polymerizations achieve a steady-state after a period, which may be at most a minute. The right side of Eq. 3-23 represents the rate of termination. There is no speci cation as to whether termination is by coupling or disproportionation since both follow the same kinetic espression. The use of the factor of 2 in the termination rate equation follows the generally accepted convention for reactions destroying radicals in pairs. It is also generally used for reactions creating radicals in pairs as in Eq. 3-13. This convention is now the IUPACpreferred convention. In using the polymer literature, one should be aware that the factor of 2 has not always been followed. Rearrangement of Eq. 3-23 to



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0' =

M Ri 2kt 1=2 3-24

(3.102)

Rp kp M Ri 2kt 1=2 3-25

Now (3.42) and (3.43) cannot depend on our particular choice of coordinates, so they must remain valid in the left-handed coordinate system: that is,

for the rate of polymerization. It is seen that Eq. 3-25 has the signi cant conclusion of the dependence of the polymerization rate on the square root of the initiation rate. Doubling the rate of initiation does not double the polymerization rate; the polymerization rate is increased p only by the factor 2. This behavior is a consequence of the bimolecular termination reaction between radicals. 3-3c Experimental Determination of Rp

O'F'





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It is appropriate at this point to brie y discuss the experimental procedures used to determine polymerization rates for both step and radical chain polymerizations. Rp can be experimentally followed by measuring the change in any property that differs for the monomer(s) and polymer, for example, solubility, density, refractive index, and spectral absorption [Collins et al., 1973; Giz et al., 2001; McCaffery, 1970; Stickler, 1987; Yamazoe et al., 2001]. Some techniques are equally useful for step and chain polymerizations, while others are more appropriate for only one or the other. Techniques useful for radical chain polymerizations are generally applicable to ionic chain polymerizations. The utility of any particular technique also depends on its precision and accuracy at low, medium, and high percentages of conversion. Some of the techniques have the inherent advantage of not needing to stop the polymerization to determine the percent conversion, that is, conversion can be followed versus time on the same reaction sample. 3-3c-1 Physical Separation and Isolation of Reaction Product

= ",2 A',

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This technique involves isolating (followed by drying and weighing) the polymer from aliquots of the polymerization system as a function of reaction time. Polymer is typically isolated by precipation by addition of a nonsolvent. The technique is primarily useful for chain polymerizations, which consist of monomer and high-molecular-weight polymer, differing greatly in their solubility. It is not generally useful for step polymerization, since they consist of monomers and a range of different low-molecular-weight products (until very high conversions) whose solubility differences are typically not too different. Even when applicable, the technique is very time-consuming and requires great care to obtain accurate results. A modi cation of this technique, applicable to many step polymerizations, involves the continuous monitoring of the small-molecule by-product. For example, for polyesteri cation between a diol and diacid above 100 C, water distills out of the reaction vessel and its volume can be measured by condensation and collection in a calibrated trap. 3-3c-2 Chemical and Spectroscopic Analysis

Additions to the text appear underlined and in colour. Word marks deleted text with a strikethrough.

O'A' = F'.

Chemical analysis of the unreacted monomer functional groups as a function of time is useful for step polymerizations. For example, polyesteri cation can be followed accurately by titration of the carboxyl group concentration with standard base or analysis of hydroxyl groups by reaction with acetic anhydride. The rate of chain polymerization of vinyl monomers can be followed by titration of the unreacted double bonds with bromine.

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