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in polymerization rate. Similar results are found for divalent counterions such a barium and strontium [de Groof et al., 1975, 1977; Mathis and Francois, 1978; Mathis et al., 1978]. Triple ion formation decreases with increasing molecular weight of the two-ended dicarbanion; thus, Rp increases with conversion. As the length of the intramolecular chain between the two anion centers increases, the probability of cyclization to the triple ion decreases. The higher reactivity of 2-vinylpyridine relative to styrene has been attributed to a combination of intramolecular solvation and triple-ion formation [Sigwalt, 1975; Soum et al., 1977].



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5-4 BLOCK AND OTHER POLYMER ARCHITECTURES Anionic and cationic living polymerizations offer routes to block copolymers, star polymers, telechelic polymers, and other polymers [Charleux and Faust, 1999; Hadjichristidis et al., 2002]. 5-4a Sequential Monomer Addition

Then Patm{r) =

Sequential addition of monomer works well in anionic polymerization for producing wellde ned block copolymers [Morton, 1983; Morton and Fetters, 1977; Quirk, 1998; Rempp et al., 1988]. An AB diblock copolymer is produced by polymerization of monomer A to completion using an initiator such as butyllithium. Monomer B is then added to the living polyA carbanions. When B has reacted completely a terminating agent such as water or

d 3 k - - {I - ik . r}





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considerations is that the reactivity of a functional group will be independent of the size of the molecule to which it is attached. Exceptions to this occur when the reactivities of the groups are very high and/or the molecular weights of the polymer are very high. The polymerization becomes diffusion-controlled in these cases because mobility is too low to allow maintenance of the equilibrium concentration of reactive pairs and of their collision frequencies. 2-1d Equivalence of Groups in Bifunctional Reactants

(211-)3

The equivalence of the reactivities of the two functional groups in bifunctional reactants has also been demonstrated in many systems. The second column in Table 2-1 shows data for the esteri cation of a homologous series of dibasic acids:

(5.60)

2-11

er V8{r)

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The rate constants tabulated are the averages of those for the two carboxyl groups in each dibasic acid. The rate constants for the two carboxyls were the same within experimental error. Further, a very important observation is that the reactivity of one of the functional groups is not dependent on whether the other has reacted. As in the case of the monocarboxylic acids, the reactivity of the carboxyl group quickly reaches a limiting value. Similar results were observed for the polyesteri cation of sebacoyl chloride (Table 2-2). It should not be concluded that the reactivity of a functional group is not altered by the presence of a second group. The data show that at small values of x up to 4 or 5, there is an effect of the second group. In most instances the effect disappears fairly rapidly with increasing molecular size as the two functional groups become isolated from each other. Thus the rate constant for the esteri cation of the dibasic acid with x 6 is the same as that for the monobasic acids. It might appear at rst glance that polymerizations involving bifunctional reagents with low x values would present a problem. However, the difference in reactivities of the functional groups of a bifunctional reagent compared to the functional group in a monofunctional reagent is not an important consideration in handling the kinetics of step polymerization. The most signi cant considerations are that the reactivity of a functional group in a bifunctional monomer is not altered by the reaction of the other group, and that the reactivities of the two functional groups are the same and do not change during the course of the polymerization.

Click Text Filters or Number Filters. Click Custom Filter. In the Custom AutoFilter dialog box, you can select operators and values to apply to the filtered data. In this case, the filter displays all records whose Contact field contains the values Francois Boisson or Fred Garvin.

(5.61)

2-2 KINETICS OF STEP POLYMERIZATION Consider the polyesteri cation of a diacid and a diol to illustrate the general form of the kinetics of a typical step polymerization. Simple esteri cation is a well-known acidcatalyzed reaction and polyesteri cation follows the same course [Otton and Ratton, 1988; Vancso-Szmercsanyi and Makay-Bodi, 1969]. The reaction involves protonation of the carboxylic acid,

= V . {er8{r)}.

OH C OH (A )

2-12

So the atom produces the polarization P{r) = er8{ r), which means thatthe quantized point dipole we wanted to determine is given by

2-13

(5.62)

2-14

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