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- W3021088185 abstract "Publisher SummaryThis chapter discusses various polyolefin processes and examples. The active site in chain-growth polymerizations can be an ion instead of a free radical. Ionic reactions are much more sensitive than free-radical processes to the effects of solvent, temperature, and adventitious impurities. Successful ionic polymerizations must be carried out much more carefully than normal free-radical syntheses. Consequently, a given polymeric structure will ordinarily not be produced by ionic initiation if a satisfactory product can be made by less expensive free-radical processes. Styrene polymerization can be initiated with free radicals or appropriate anions or cations. Commercial atactic styrene polymers are, however, all almost free-radical products. Particular anionic processes are used to make research-grade polystyrenes with exceptionally narrow molecular weight distributions and the syndiotactic polymer is produced by metallocene catalysis. Cationic polymerization of styrene is not a commercial process. It is well known in organic chemistry that the reactivities of these various forms of organic ions and counterions may differ significantly, and it is thus not surprising that the same influences are detectable in ionic polymerizations. In general, propagation rates are higher the more the inacroion and its counterion are separated. Steric control of the polymer microstructure is greater, however, when the macroion and the counterion are associated. Rates of ionic polymerizations are by and large much faster than in free-radical processes. This is mainly because termination by mutual destruction of active centers occurs only in free-radical systems." @default.
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- W3021088185 date "1982-01-01" @default.
- W3021088185 modified "2023-09-27" @default.
- W3021088185 title "Ionic and Coordinated Polymerizations" @default.
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- W3021088185 doi "https://doi.org/10.1016/b978-0-12-601680-2.50013-2" @default.
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