By Michael Szwarc, Marcel Van Beylen (auth.)
More than just an up to date assessment of ionic polymerization, this ebook offers an in-depth and important comparability of the anionic and cationic polymerization of vinyl monomers and heterocyclic compounds. those various modes of ionic polymerization are tested with reference to their skill for generating dwelling polymers. the concept that of dwelling polymers is re-examined and redefined in mild of present wisdom of ionic polymerization and attainable aspect reactions. all through, the authors provide perceptive insights into the elemental techniques of polymerization chemistry and polymerization response mechanisms. The ebook starts off with a overview of ionic and radical polymerizations, the advance of ionic polymerization, dwelling and dormant polymers, and polymerizability. It is going directly to think about very important elements of the constitution and houses of ionic species; initiation and propagation of ionic polymerization; polymerization steps except initiation or propagation, similar to termination, isomerization, move, backbiting, and degraduation; and ionic copolymerization. Ionic Polymerization and residing Polymers is a miles wanted complex textual content that may be broadly learn and observed by way of polymer scientists, macromolecular chemists, and fabrics scientists.
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Extra info for Ionic Polymerization and Living Polymers
Proton transfer from a covalent acid to a covalent base is the most common example of such a process. Thus anhydrous perchloric acid reacts with an equimolar amount of water yielding a crystalline ionic salt, H30 +, CI04"; the nonconducting solution of HBr in sulfur dioxide becomes conducting on addition of an cquimolar amount of water due to the formation of free H30 + and Br- ions. Transfer Ionic Species I 41 of other charged moieties leads also to the formation of ions. For example, the transfer of Cl- from benzyl chloride to boron trichloride yields in methylene chloride solution the PhCHt, BCli ion pairs; the transfer of OH- from triphenylmethyl carbinol dissolved in liquid sulfur dioxide to a solvent molecule yields the Ph3C+ cations and HS0"3 anions, and so forth.
These effects of solvents and of the initial monomer concentration on the equilibrium monomer concentration are shown in Fig. 6. Not surprising, but neither immediately expected is the influence of the initiator upon the equilibrium concentration of the monomer in the experiments involving living polymers. The end-groups of living polymers are ionic (salts) and their concentration (living polymers) affects the activity coefficients of the growing end-groups of the living polymers. Neglect of that effect led in the past to a controversy.
6, 93. 47. V. 1965. J. Polym. Sci. A3, 3261. 48. , and Teyssie P. 1967. Polym. Lett. 85, 789. 49. V. 1983. J. Am. Chern. Soc. 105,5706. 50. , and Higashimura, T. 1984. Macromolecules 17, 265, 2228. , and Higashimura, T. 1986. Macromolecules 20, 916, 2693. 51. P. 1986. Polym. Bull. 15, 317. P. 1987. Polym. Bull. 17,7. P. 1987. J. Macromol. Sci. A24, 933. Introduction /37 52. H. 1986. J. Am. Chern. Soc. 108, 733. 53. Szwarc, M. 1987. E. Hogen-Esch and J. ), Recent Advances in Anionic Polymerization, p.
Ionic Polymerization and Living Polymers by Michael Szwarc, Marcel Van Beylen (auth.)