By L. J. Ferry
This exhaustive reference textual content systematically introduces the elemental theories and experimental tools of anionic polymerization in addition to the synthesis, research, and features of anionically polymerized items.
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Extra info for Anionic Polymerization
Calorimetric measurements 89) on the interaction of T M E D A with poly(isoprenyl)lithium have yielded data that are not inconsistent with the formation of a complex between one molecule of the former and two of the latter. At the low level of T M E D A used, equilibrium (45) is not likely to be of any significance but all the other equilibria must be considered. It is clear from the results of the SEC study that several species propagate and that at --30 °C the exchange among these is quite slow.
It has been suggested to7) that the failure of t-butyltithium to react completely with styrene is due to an impurity (undefined). An alternative explanation of this retarded reactivity could focus on the structure, and energetics, of the crossassociated complex (or complexes) formed between t-butyllithium and styryllithium. It is, though, currently impossible to quantitatively define the role that such crossassociated organolithium species play in these initiation events. (C2HsLi) 3. Furthermore, the bonding energetics of these cross-aggregated structures involving the allylic or benzylic active centers with alkyllithiums have not yet been examined.
The validity of the viscosity measurements regarding the reported 52> influence of anisole and diphenyl ether on the association of the poly(styryl)lithium dimers has, though, been questioned 78,160,161). Suffice it to note that the fallacies in the data provided 160,161>have been commented upon elsewhere 162). Even though it is wellknown that ethereal solvents can interact with organolithium compounds, no explanation was given 78,160,161) as to why aromatic ethers should be completely exempt from this general behavior.