Tetrahydrofuran polymerization hydride abstraction

Use of triphenylmethyl and cycloheptatrienyl cations as initiators for cationic polymerization provides a convenient method for estimating the absolute reactivity of free ions and ion pairs as propagating intermediates. Mechanisms for the polymerization of vinyl alkyl ethers, N-vinylcarbazole, and tetrahydrofuran, initiated by these reagents, are discussed in detail. Free ions are shown to be much more reactive than ion pairs in most cases, but for hydride abstraction from THF, triphenylmethyl cation is less reactive than its ion pair with hexachlorantimonate ion. Propagation rate coefficients (kP/) for free ion polymerization of isobutyl vinyl ether and N-vinylcarbazole have been determined in CH2Cl2, and for the latter monomer the value of kp is 10s times greater than that for the corresponding free radical polymerization. 

Initiation with Tropylium Ion. When cycloheptatrienyl hexachlor-antimonate is used as initiator for tetrahydrofuran polymerization, the reactions are somewhat cleaner, and strong colors do not develop as readily as when the corresponding trityl salts are used (17). Rates of initiation are much lower, and the reaction is hardly noticeable at room temperature. However, at 50 °C. and above initiation is significant, and the polymerizations proceed almost to the expected theoretical conversion of monomer to polymer even when hexachlorantimonate is the anion (Table III). Therefore, the apparent low equilibrium conversion obtained with the rapidly initiating trityl salts is minimized in this case by the comparatively low rate of consumption of initiator. Once again GLC demonstrates clearly that the initiation reaction involves primarily hydride abstraction from the ether. 

With some cationic initiators, such as the triphenyl methyl (trityl) salts of the general formula PhsC " X , where X is a stable anion such as CIO4, SbClg, and PFg, the initiation does not involve direct addition to monomer. The carbocation abstracts a hydride (H ) ion from the a-carbon of the monomer and the resulting new carbocation initiates polymerization. Thus the reaction of trityl hexafluo-rophosphate and tetrahydrofuran has been shown to proceed as follows (Cowie, 1991) ... 

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See also in sourсe #XX -- [ ]

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