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For many of the alkene monomers, the equilibrium position for the propagation depropagation equilibrium is far to the right under the usual reaction temperatures employed, that is, there is essentially complete conversion of monomer to polymer for all practical purposes Table 3-16 shows the monomer concentrations at 25 C for a few monomers [Cook et al, 1958; McCormick, 1957; Wall, 1960; Worsfold and Bywater, 1957] Data are also shown for the ceiling temperatures of the pure monomers The data do indicate that the polymer obtained in any polymerization will contain some concentration of residual monomer as determined by Eq 3-178 Further, there are some monomers for which the equilibrium is not particularly favorable for polymerization, for example, a-methylstyrene Thus at 25 C a 22-M solution of a-methylstyrene will not undergo polymerization Pure a-methylstyrene will not polymerize at 61 C.



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w=cJk 2 +J1-2,

Methyl methacrylate is a borderline case in that the pure monomer can be polymerized below 220 C, but the conversion will be appreciably less than complete For example, the value of M c at 110 C is 014 M [Brandrup and Immergut, 1989] Equation 3-178 applies equally well to ionic chain and ring-opening polymerizations as will be seen in subsequent chapters The lower temperatures of ionic polymerizations offer a useful route to the polymerization of many monomers that cannot be polymerized by radical initiation because of their low ceiling temperatures The successful polymerization of a previously unpolymerizable monomer is often simply a matter of carrying out the reaction at a temperature below its ceiling temperature Interestingly, it should not be assumed that a polymer will be useless above its ceiling temperature.

and another with negative frequency,





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A dead polymer that has been removed from the reaction media will be stable and will not depolymerize unless an active end is produced by bond cleavage of an end group or at some point along the polymer chain When such an active site is produced by thermal, chemical, photolytic, or other means, depolymerization will follow until the monomer concentration becomes equal to M c for the particular temperature The thermal behavior of many polymers, however, is much more complex Degradative reactions other than depolymerization will often occur at temperatures below the ceiling temperature..

(3.65)

3-9c-2

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The ceiling temperature phenomenon is observed because H is highly exothermic, while S is mildly exoentropic. The opposite type of phenomenon occurs in rare instances where S is endoentropic ( S ) and H is very small (either or ) or zero. Under these conditions, there will be a oor temperature Tf below which polymerization is not possible. This behavior has been observed in only three cases the polymerizations of cyclic sulfur and selenium octamers and octamethylcyclotetrasiloxane to the corresponding linear polymers (Secs. 7-11a). H is 9.5, 13.5, and 6.4 kJ mol 1 , respectively, and S is 27, 31, and 190 J K 1 mol 1 , respectively [Brandrup et al., 1999; Lee and Johannson, 1966, 1976].

= -cJk 2 + J1-2.

Radical chain polymerizations are characterized by the presence of an autoacceleration in the polymerization rate as the reaction proceeds [North, 1974]. One would normally expect a reaction rate to fall with time (i.e., the extent of conversion), since the monomer and initiator concentrations decrease with time. However, the exact opposite behavior is observed in many polymerizations the reaction rate increases with conversion. A typical example is shown in Fig. 3-15 for the polymerization of methyl methacrylate in benzene solution [Schulz and Haborth, 1948]. The plot for the 10% methyl methacrylate solution shows the behavior that would generally be expected. The plot for neat (pure) monomer shows a dramatic autoacceleration in the polymerization rate. Such behavior is referred to as the gel effect. (The term gel as used here is different from its usage in Sec. 2-10; it does not refer to the formation of a crosslinked polymer.) The terms Trommsdorff effect and Norrish Smith effect are also used in recognition of the early workers in the eld. Similar behavior has been observed for a variety of monomers, including styrene, vinyl acetate, and methyl methacrylate [Balke and Hamielec, 1973; Cardenas and O Driscoll, 1976, 1977; Small, 1975; Turner, 1977; Yamamoto and Sugimoto, 1979]. It turns out that the gel effect is the normal

(3.66)

Fig. 3-15 Autoacceleration in benzoyl peroxide initiated polymerization of methyl methacrylate in benzene at 50 C. The different plots represent various concentrations of monomer in solvent. After Schulz and Haborth [1948] (by permission of Huthig and Wepf Verlag, Basel).

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