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copolymerization is used to show the analogy between the curves in Fig. 6-1 and those for vapor liquid equilibria in ideal liquid mixtures. The copolymer is richer in M1 when r1 > 1 and is poorer in M1 when r1 < 1. One can distinguish between extreme and moderate ideal behavior depending on the difference between r1 and r2 . Extreme ideal behavior occurs when r1 and r2 are very different (e.g., 10 and 1). Moderate ideal behavior occurs when r1 and r2 are not too different, (e.g., 0.5 and 2). The term ideal copolymerization does not in any sense connote a desirable process. An important consequence of ideal copolymerizations is that it becomes progressively more dif cult to produce copolymers containing appreciable amounts of both monomers as the difference in r1 and r2 increases, that is, as one progresses from moderate to extreme ideal behavior. When, for example, r1 10 and r2 0:1, copolymers containing appreciable amounts of M2 cannot be obtained. Thus a comonomer feed composition of 80 mol% M2 f2 0:8 would yield a copolymer containing only 18.5 mol% M2 (F2 0:185). It is only when r1 and r2 do not differ markedly (e.g., r1 0:5 2) that there will exist a larger range of comonomer feed compositions, which yield copolymers containing appreciable amounts of both monomers. 6-2d-2 Alternating Copolymerization: r 1 r 2 0



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Alternating copolymerization is characterized by r1 r2 0, where neither r1 nor r2 is greater than one. As with ideal behavior, there are two types of alternating behavior extreme and moderate alternating behavior. Both r1 and r2 are zero in extreme alternating behavior, and the two monomers enter into the copolymer in equimolar amounts in a nonrandom, alternating arrangement along the copolymer chain. Each of the two types of propagating species * * preferentially adds the other monomer, that is, M1 adds only M2 and M2 adds only M1. The copolymerization equation reduces to

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The copolymer has the alternating structure I irrespective of the comonomer feed composition. Moderate alternating behavior occurs when either (1) both r1 and r2 are small (r1 r2 very small, close to 0) or (2) one r value is small and the other r is zero (r1 r2 0). The copolymer composition tends toward alternation but is not the perfectly alternating structure I . The behavior of most comonomer systems lies between the two extremes of ideal and alternating copolymerization. As the r1 r2 product decreases from one toward zero, there is an increasing tendency toward alternation. Perfect alternation occurs when r1 and r2 are both zero. The tendency toward alternation and the tendency away from ideal behavior increases as r1 and r2 become progressivley less than unity. The range of behaviors can be seen by considering the situation where r2 remains constant at 0.5 and r1 varies between 2 and 0. Figure 6-2 shows the copolymer composition as a function of the feed composition in these cases. The curve for r1 2 shows the ideal type of behavior described previously. As r1 decreases below 2, there is an increasing tendency toward the alternating behavior with each type of propagating species preferring to add the other monomer. The increasing

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(6.27)

Fig. 6-2 Dependence of the instantaneous copolymer composition F1 on the initial comonomer feed composition f1 for the indicated values of r1 , where r2 is constant at 0.5. After Walling [1957] (by permission of Wiley, New York) from plot in Mayo and Walling [1950] (by permission of American Chemical Society, Washington, DC).

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alternation tendency is measured by the tendency of the product r1 r2 to approach zero. Of great practical signi cance is the fact that a larger range of feed compositions will yield copolymers containing sizable amounts of both monomers. However, when r1 r2 is very small or zero the alternation tendency is too great and the range of copolymer compositions that can be obtained is again limited. In the extreme case where both r1 and r2 are zero, only the 1 : 1 alternating copolymer can be produced. This would show in Fig. 6-2 as a horizontal line at F1 0:5 (but the line would not touch either the left or right ordinates). The plots in Fig. 6-2 illustrate an interesting characteristic of copolymerizations with a tendency toward alternation. For values of r1 and r2 both less than unity, the F1 =f1 plots cross the line representing F1 f1 . At these interesections or crossover points the copolymer and feed compositions are the same and copolymerization occurs without a change in the feed composition. Such copolymerizations are termed azeotropic copolymerizations. The condition under which azeotropic copolymerization occurs, obtained by combination of Eq. 6-12 with d M1 =d M2 M1 = M2 , is

A special situation arises when one of the monomer reactivity ratios is much larger than the other. For the case of r1 ) r2 (i.e., r1 ) 1 and r2 ( 1), both types of propagating species preferentially add monomer M1. There is a tendency toward consecutive homopolymerization of the two monomers. Monomer M1 tends to homopolymerize until it is consumed; monomer M2 will subsequently homopolymerize. An extreme example of this type of behavior is shown by the radical polymerization of styrene-vinyl acetate with monomer reactivity ratios of 55 and 0.01. (See Sec. 6-3b-1 for a further discussion of this comonomer system.) 6-2d-3 Block Copolymerization: r 1 > 1; r 2 > 1

(6.28)

If both r1 and r2 are greater than unity (and therefore, also r1 r2 > 1) there is a tendency to form a block copolymer (structure II ) in which there are blocks of both monomers in the chain. This type of behavior is rarely encountered. 6-2e Variation of Copolymer Composition with Conversion

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