By Frederick R. Eirich (Auth.)
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Extra resources for Science and Technology of Rubber
The chlorine substituent apparently imparts a marked reactivity to this monomer, since it polymerizes very much more rapidly than butadiene, isoprene, or any other dienes. In fact, chloroprene is even more susceptible to free radical polymerization than styrene, and requires a powerful inhibitor for stabilization. It polymerizes extremely rapidly in emulsion systems, so that its rate must be carefully controlled. Various recipes [24, 25] can be used for emulsion polymerization of chloroprene, with potassium persulfate as a popular initiator.
CH2 V The cationic polymerization of tetrahydrofuran, although not leading directly to a commercial elastomer, deserves special attention because of its kinetic features. , it does not exhibit any termination step, very much like the analogous anionic polymerizations which are discussed in Section VIII. This is rather remarkable, in view of the known high reactivity of carbenium ions and their propensity to participate in various side reactions during polymerization. This remarkable stability of the growing chain in the cationic polymerization of cyclic ethers has been ascribed  to an "oxonium" ion mechanism, whereby the carbenium ion is actually "solvated" by coordination with the oxygen of the monomer, as follows: Initiation R+ + O ^ I -+ R — O ^ I (48) 54 MAURICE MORTON Propagation R—Ο^ [ + Ο^ I ^ · · - ^ R— [Q(CH2)4L—Q(CH2)3CH2—6^ | (49) where R + is the initiating cation.
The figure shows the various loci in which monomer is found, and which compete with each other for the available free radicals. Thus, in the initial stages, the monomer is found in three loci: (a) in aqueous solution, (b) as emulsified droplets, and (c) within the soap micelles. Both the dissolved monomer and the relatively large monomer droplets represent minor loci for reaction with the initiator radicals (except, of course, in the case of highly water-soluble monomers). However, the large number of soap micelles containing imbibed monomer represent a statistically important locus for initiation of polymerization.