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In contrast to the kinetic approach, deviations from the terminal model have also been treated from a thermodynamic viewpoint [Kruger et al., 1987; Lowry, 1960; Palmer et al., 2000, 2001]. Altered copolymer compositions in certain copolymerizations are accounted for in this treatment in terms of the tendency of one of the monomers (M2) to depropagate. An essential difference between the kinetic and thermodynamic treatments is that the latter implies that the copolymer composition can vary with the concentrations of the monomers. If the concentration of monomer M2 falls below its equilibrium value [M]c at the particular reaction temperature, terminal M2 units will be prone to depropagate. The result would be a



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[ek, el, 1= ow,

Fig. 6-12 Plot of F1 versus f1 for copolymerization of styrene (M1) and diethyl fumarate (M2). The solid line represents the terminal model with r1 0:22, r2 0:021. After Ma et al. [2001] (by permission of American Chemical Society, Washington, DC); an original plot, from which this gure was drawn, was kindly supplied by Dr. T. Fukuda.

and diagonalizing flo,

Fig. 6-13 Plot of propagation rate constant versus f1 for copolymerization of styrene (M1) and diethyl fumarate (M2). The dotted line represents the terminal model with r1 0:22, r2 0:021 (i.e., s1 s2 1). The solid line represents the implicit penultimate model with s1 0:055, s2 0:32. After Ma et al. [2001] (by permission of American Chemical Society, Washington, DC); an original plot, from which this gure was drawn, was kindly supplied by Dr. T. Fukuda.

(7.38) (7.39)





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decrease in the amount of this monomer in the copolymer. The kinetic approach does not predict any dependence of the copolymer composition on the monomer concentration. Further, the thermodynamic approach differs from the kinetic approach in that the former emphasizes the temperature dependence of the copolymer composition since the polymerization depolymerization equilibrium is temperature-dependent. (The penultimate model does not, however, predict the copolymer composition to be independent of temperature. The effect of temperature in the penultimate model comes from the variation of the four monomer reactivity ratios and two radical reactivity ratios with temperature.) The present discussion will be almost completely limited to copolymerizations in which only one of the monomers has a tendency to depropagate. systems in which both monomers tend to depropagate are dif cult to treat mathematically and also involve a large number of unknown parameters. Different types of copolymerization behavior can be considered depending on whether one assumes penultimate effects on the depropagation reaction. Thus Lowry [1960] considers two different cases in which monomer M1 has absolutely no tendency to depropagate irrespective of the preceding units in the chain, while monomer M2 has no tendency to depropagate if it is attached to an M1 unit. The two cases differ in the different tendencies of monomer M2 to depropagate. In case I, M2 tends to depropagate if it is attached to another M2 unit:

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You can change the alignment of text. Select the text that you want to edit and click the Home tab on the Ribbon. Click an alignment button: Align Left ( ), Center ( ), Align Right ( ) or Justify ( ).

[ek' flo]

6-80

(7.40)

In case II, M2 tends to depropagate only when it is attached to a sequence of two or more M2 units:

From (7.3), (7.15), (7.37), (7.38), and (7.40), we find that"

6-81

~ (vj + uj) ,

* * * Thus M1M2 does not depropagate in case I, while neither M1M2 nor M1M2M2 depropagate in case II. The copolymer composition for case I is given by [Kruger et al., 1987; Lowry, 1960; Szymanski, 1987]

d M1 r1 M1 M2 1 a d M2 M2 6-82

~ (vj - uj) ,

0 #1=2 1 & ' "& ' 1@ K M1 K M1 2 A a 4K M2 1 K M2 1 K M2 2 r2 r2 6-83

= Ok Vl,

where K is the equilibrium constant for the equilibrium in Eq. 6-80. The copolymer composition for case II is given by

You may choose to insert slides containing a predefined layout. You can customise the slide layout, however, by adding a new text box to it. A text box is simply a receptacle for text in a slide. (For help adding text to a text box, refer to the section Add and Edit Slide Text earlier in this chapter.) When you add a new text box to a slide, you can control the placement and size of the box. (For help moving and resizing text boxes and other slide objects, see the sections Move a Slide Object and Resize a Slide Object later in this chapter.)

(7.41) (7.42) (7.43)

6-84

(7.44)

6-85

O~ -w2 k 2GOk vl, O~ - w 2 k 2Gwo vl,

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