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(There are a few reports of initiation by primary or secondary halides [Toman et al, 1989a,b], but initiation more likely involves self-ionization of the Lewis acid or the presence of adventitious water) Tertiary carbocations such as t-butyl and 2-phenyl-isopropyl (cumyl) are suf ciently stable to form but are not more stable than the carbocations derived from their additions to monomers such as isobutylene, styrene, or N-vinylcarbazole, so that polymerizations of those monomers occur Cumyl and t-butyl carbocations have been generated from cumyl and t-butyl esters and ethers as well as from the halides [Faust and Kennedy, 1987; Mishra and Kennedy, 1987] Highly stable carbocations such as trityl, f3 C and cycloheptatrienyl (tropylium), C7 H are generally too 7.



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(4.44) (4.45)

stable to be very ef cient in polymerizing the less reactive monomers such as isobutylene and styrene but polymerization of the more reactive monomers (p-methoxystyrene, vinyl ethers, indene, N-vinylcarbazole) proceeds rapidly [Ledwith, 1979a,b; Rooney, 1978]. (Trityl and tropylium carbocations are suf ciently stable that their salts with stable anions such as hexa uoroantimonate, SbF , can be purchased in pure crystalline form from chemical vendors.) 6 Acylium ions (oxacarbocations) have also been used to initiate cationic polymerization [Sawamoto et al., 1977, 1978]. These can be formed in situ or separately prepared as the solid salt, which is subsequently added to the monomer solution:

(a)k (at)!

R C +(SbF6 )

as (4.46)

5-6





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Many polymerizations exhibit a maximum polymerization rate at some ratio of initiator to coinitiator [Biswas and Kabir, 1978, 1978; Colclough and Dainton, 1958; Taninaka and Minoura, 1976]. The polymerization rate increases with increasing [initiator]/[coinitiator], reaches a maximum, and then either decreases or levels off. Figure 5-1 shows this behavior for the polymerization of styrene initiated by tin(IV) chloride water in carbon tetrachloride. The decrease in rate at higher initiator concentration is usually ascribed to inactivation of the coinitiator by initiator. The inactivation process in a system such as SnCl4 -H2 O may involve hydrolysis of Sn bonds to Sn Cl OH. There is experimental evidence for such reactions when comparable concentrations of coinitiator and initiator are present. However, the rate maxima as in Fig. 5-1 are observed at quite low [initiator]/[coinitiator] ratios where corresponding experimental evidence is lacking. An alternate mechanism for the behavior in Fig. 5-1 is that initiator, above a particular concentration, competes successfully with monomer for the initiator coinitiator complex (V) to yield the oxonium salt (VI), which

(a)k (at)!

5-7

(n + 1 + l)! In + l - k)(nl. In!(n + l- k)!

Fig. 5-1 Effect of water concentration on the SnCl4 -initiated polymerization rate of styrene in carbon tetrachloride at 25 C. Symbols * and * refer to initiator concentrations of 0.08 and 0.12 M, respectively. After Colclough and Dainton [1958] (by permission of the Faraday Society and Royal Society of Chemistry, London).

Now, substituting (4.46) in (4.43) and changing the summation dummy indices land k to m and j, where j == l + k and m == n + l - k, we find that

is too unreactive in protonating ole ns because the basicity of the carbon carbon double bond is far less than that of water [Ledwith and Sherrington, 1974] (see also Sec. 5-2c-4). The optimum initiator to coinitiator ratio varies considerably depending on the initiator, coinitiator, monomer, solvent, and temperature, since these factors affect the balance between the competing processes of initiation and inactivation. Initiation by some organotransition metal complexes involves addition of a positive metallic site to monomer [Baird, 2000]. For example, the complex formed from cyclopentadienyltrimethyltitanium and triper uorophenyl boron initiates polymerization by the sequence

00 00 00 00

5-2a-3

cn,mlm)(nl,

Chlorine, bromine, and iodine act as cationogens in the presence of the more active Lewis acids such as trialkylaluminum or dialkylaluminum halide [DiMaina et al., 1977; Magagnini et al., 1977]. The initiating species is the halonium ion X present in low concentration via the equilibrium reaction between Lewis acid and halogen. Iodine is unique among the halogens in that it initiates polymerization of the more reactive monomers (styrene, vinyl ether, acenaphthylene. N-vinylcarbazole) even in the absence

(4.47)

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