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(4.116) (4.117)

LCP can be restored in the more polar solvent by the addition of tetra-n-butylammonium iodine Highly nucleophilic counterions such as chloride often push the equilibrium so far toward the covalent species that neither living or nonliving polymerization occurs The occurrence of a narrow size distribution is diagnostic of a living polymerization In reaction systems where one passes from nonliving to living polymerization by changes in coinitiator, temperature, solvent, added nucleophile, or added salt, one observes a shift from a unimodal molecular weight distribution (PDI considerably above 1; theoretical PDI 2 as per Sec 3-11a and Eq 2-97) for nonliving polymerization to a bimodal distribution for a mixture of living and nonliving polymerizations to a unimodal distribution (PDI close to 1) for living polymerization The rates and molecular weights for the living polymerizations are lower than those for the nonliving polymerizations.

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The latter proceed by freeion and ion-pair centers that are much more reactive than the propagating species in living systems A range of molecular weights has been obtained in the various living systems Some studies have concentrated on the synthesis of low-molecular-weight telechelic polymers with molecular weights of only a few thousand, while polymers of number-average molecular weights up to 50,000 100,000 have been synthesized in other studies The formation of Poisson distributions is corroboration of the fast equilibrium assumed between active and inactive propagating centers For any propagating center, the fractions of its total lifetime spent as active and inactive centers are very close to those for other propagating centers None of the cationic living polymerization systems are as long-lived as the anionic systems to be described in Sec 5-3b-1.

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The various cationic living systems show the characteristics of living systems as long as monomer is present, but decay of propagating species begins in the absence of monomer The half-lives for propagating species in the absence of monomer vary from less than an hour to many hours at the higher temperatures but were as high as a day or more for lower temperatures depending on the particular system [Choi et al, 1990; Higashimura and Sawamoto, 1989] The lifetimes for the isobutylene systems appear to be lower than those for other monomers, probably only minutes..

+ .6.0.1 (15) + i .6.0.2(15).

Cationic polymerizations, like their radical counterparts, are quite exothermic, since the reaction involves the conversion of p-bonds to s-bonds. The heat of polymerization for any particular monomer is essentially the same irrespective of the mode of initiation (if the monomer can be polymerized by both radical and cationic initiators). From a consideration of Eqs. 5-34 and 5-35, the composite activation energies ER and EXn for the rate and degree of polymerization, respectively, are obtained as

(4.118)

ER Ei Ep Et EX n Ep Et 5-59 5-60

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where Ei , Ep , and Et are the activation energies for the initiation, propagation, and chain termination steps, respectively For the activation energy for X n, Et will be replaced by an Etr term or terms when transfer occurs Propagation involves the addition of an ion or ion pair to a monomer in a medium of low polarity and does not require a large activation energy (about <20 25 kJ mol 1 ) The values of Ei and Et are greater than Ep in most cases The net interaction of the various activation energies leads to values of ER in the range of 20 to 40 kJ mol 1 For many polymerization systems ER is negative and one observes the rather unusual phenomenon of increasing polymerization rates with decreasing temperatures The negative activation energy for the polymerization rate is not, however, a complete generalization.

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