e (NH3) + CH2 CHY CH2 CHY CH2 CHY in .NET

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e (NH3) + CH2 CHY CH2 CHY CH2 CHY
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The radical anion proceeds to propagate in the same manner as discussed above for initiation by sodium naphthalene. (Polymerizations in liquid ammonia are very different from those in organic solvents in that free ions probably constitute the major portion of propagating species.) Electron-transfer initiation also occurs in heterogeneous polymerizations involving dispersions of an alkali metal in monomer. Initiation involves electron transfer from the metal to monomer followed by dimerization of the monomer radical anion to form the propagating
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IONIC CHAIN POLYMERIZATION
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dianion [Fontanille, 1989; Gaylord and Dixit, 1974; Morton and Fetters, 1977]. The rate of initiation is dependent on the surface area of the metal since the reaction is heterogeneous. Increased surface area of metal is achieved by condensing metal vapors directly into a reaction mixture or as a thin coating (mirror) of the metal on the inside walls of the reaction vessel or simply using small particle size of the metal. Initiation by ionizing radiation occurs by electron transfer. Some component of the reaction system, either the solvent or monomer, undergoes radiolysis to yield a cation radical and
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solvated electron [Stannett et al., 1989]. If a monomer with an electron-withdrawing substituent is present, polymerization occurs by addition of the electron to monomer followed by dimerization to the dicarbanion and propagation (Sec. 5-2a-6). Electroinitiated polymerization proceeds by direct electron addition to monomer to generate the monomer anion radical, although initiation in some systems may involve the formation of an anionic species by electrolytic reaction of some component of the reaction system (often the electrolyte) [Olaj, 1987].
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Termination Polymerizations without Termination
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Termination of a propagating carbanion by combination with the counterion occurs in only a few instances, such as in electroinitiated polymerization when the contents of the anode and cathode chambers are mixed and in initiation by ionizing radiation. Termination by combination of the anion with a metal counterion does not take place. Many anionic polymerizations, espcially of nonpolar monomers such as styrene and 1,3-butadiene, take place under conditions in which there are no effective termination reactions. Propagation occurs with complete consumption of monomer to form living polymers. The propagating anionic centers remain intact because transfer of proton or other positive species from the solvent does not occur. Living polymers are produced as long as one employs solvents, such as benzene, tetrahydrofuran, and 1,2-dimethoxyethane, which are relatively inactive in chain transfer with carbanions. The polymerization of styrene by amide ion in liquid ammonia, one of the rst anionic systems to be studied in detail, is one of the few anionic polymerizations where chain transfer to solvent is extensive [Higginson and Wooding, 1952]. The nonterminating character of living anionic polymerization (LAP) is apparent in several different ways. Many of the propagating carbanions are colored. If a reaction system is highly puri ed so that impurities are absent, the color of the carbanions is observed to persist throughout the polymerization and does not disappear or change at 100% conversion. Further, after 100% conversion is reached, additional polymerization can be effected by adding more monomer, either the same monomer or a different monomer. The added monomer is also polymerized quantitatively and the molecular weight of the living polymer is increased. 5-3b-2 Termination by Impurities and Deliberately Added Transfer Agents
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Most anionic (as well as cationic) polymerizations are carried out in an inert atmosphere with rigorously cleaned reagents and glassware since trace impurities lead to termination [Hadjichristidis et al., 2000]. Moisture absorbed on the surface of glassware is usually removed by
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ANIONIC POLYMERIZATION OF THE CARBON CARBON DOUBLE BOND
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aming under vacuum or washing with a living polymer solution. Oxygen and carbon dioxide from the atmosphere add to propagating carbanions to form peroxy and carboxyl anions. These are normally not reactive enough to continue propagation. (The peroxy and carboxyl anions usually are nally obtained as HO and HOOC groups when a proton donor is subsequently added to the polymerization system.) Any moisture present terminates propagating carbanions by proton transfer:
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