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The stability of polystyryl carbanions is greatly decreased in polar solvents such as ethers. In addition to hydride elimination, termination in ether solvents proceeds by nucleophilic displacement at the C bond of the ether. The decomposition rate of polystyryllithium O in THF at 20 C is a few percent per minute, but stability is signi cantly enhanced by using temperatures below 0 C [Quirk, 2002]. Keep in mind that the stability of polymeric carbanions in the presence of monomers is usually suf cient to synthesize block copolymers because propagation rates are high. The living polymers of 1,3-butadiene and isoprene decay faster than do polystyryl carbanions. 5-3b-4 Termination and Side Reactions of Polar Monomers



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J = atP'

Polar monomers, such as methyl (meth)acrylate, methyl vinyl ketone, and acrylonitrile, are more reactive than styrene and 1,3-dienes because the polar substituent stabilizes the carbanion propagating center by resonance interaction to form the enolate anion. However, the polymerizations are more complicated than those of the nonpolar monomers because the polar





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substituents (ester, ketone, nitrile) are reactive toward nucleophiles. This leads to termination and side reactions competitive with both initiation and propagation, resulting in complex polymer structures and major dif culties in achieving living polymerizations [Bywater, 1975, 1985; Hogen-Esch and Smid, 1987; Muller et al., 1986; Quirk, 1995, 1998, 2002; Vleck and Lochmann, 1999; Warzelhan et al., 1978; Zune and Jerome, 1999]. Several different nucleophilic substitution reactions have been observed in the polymerization of methyl methacrylate. Attack of initiator on monomer converts the active alkyllithium to the less active alkoxide initiator (Eq. 5-75). Further, methyl methacrylate (MMA) is converted to isopropenyl alkyl ketone to the extent that this reaction occurs.

P(r) = p8(r).

2-9

(5.12)

It is evident that, although there is a decrease in reactivity with increased molecular size, the effect is signi cant only at a very small size. The reaction rate constant very quickly reaches a limiting value at x 3, which remains constant and independent of molecular size. Analogous results are found for the polyesteri cation of sebacoyl chloride with a,o-alkane diols [Ueberreiter and Engel, 1977]:

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The Quick Access toolbar, which appears on-screen regardless of what tab is currently shown in the Ribbon, offers quick access to the Save, Undo and Redo commands. You can customise this toolbar to include other commands, such as the Quick Print command or another command you use often. Alternatively, you might customise the toolbar to omit commands that appear by default. By default, the Quick Access toolbar appears in the top left corner of the program window, above the Ribbon. You can choose to display the toolbar below the Ribbon instead.

In 4 when we considered the free radiation field, both E and B were transverse. Here we have to be more careful because although B is still transverse, (5.5) shows that E is no longer transverse. The longitudinal part ofE decouples from B in the equations of motion and is, in fact, a function of P only:2 EII(r)

2-10

(~)].

The rate constant for esteri cation is independent of x for the compounds studied (Table 2-2). Examples of similar behavior can be found for other reactions [Rand et al., 1965]. The results for sebacoyl chloride offer direct evidence of the concept of functional group reactivity being independent of molecular size, since the rate constant is independent of n as well as x. The independence of functional group reactivity of molecular size is contrary to the general impression that was widely held in the early years of polymer science. There was a general misconception of decreased reactivity with increased molecular size. This was due

(5.13)

TABLE 2-2 Rate Constants for Polyesteri cation (26.9 C) of Sebacoyl Chloride with a,o-Alkane Diols in Dioxanea; b Molecular Size (x) 5 6 7 8 9 10

So Ell does not not have any independent degrees of freedom and should not be quantized. The displacement vector D == E + 41TP, however, is transverse. Thus, in the present case, D and B, rather than E and B, are the right pair of field vectors that contain only the truly independent degrees of freedom of the field, and they are what we should use in the canonical quantization scheme. Rewriting Maxwell equations in terms of D and B, we find that

Rate constants are in units of L mol 1 s 1. Data from Ueberreiter and Engel [1977].

(5.14) (5.15)

in large part to the fact that reactions with the larger-sized species were often attempted without adjusting concentrations so as to have equivalent concentrations of the reacting functional groups. In many instances the low or dif cult solubility of the higher-molecular-weight reactants in a homologous series was responsible for the observed, apparent low reactivity. These effects are still pitfalls to be avoided. 2-1c Theoretical Considerations

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