Read e-book online Anionic Polymerization PDF

By L. J. Ferry

This exhaustive reference textual content systematically introduces the fundamental theories and experimental tools of anionic polymerization in addition to the synthesis, research, and features of anionically polymerized items.

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Quirk and L. J. Fetters The presence of residual initiator in the polymerization leading to the polystyrene whose distribution is shown in Fig. 8b was verified as follows los). At the completion of the polymerization, both THF and monomer were added to the system. The intensity of the absorption band of poly(styryl)lithium (~'m,x 334 rim) was found to increase to an extent which demonstrated that ca. 75 °/o of the added t-butyllithium remained at the completion of the first polymerization. These results indicated that the conventional spectroscopic method of determining the completion of the initiation reaction is fraught with potential uncertainties, insofar as the t-butyllithium-styrene system is concerned.

In an analogous study, Geerts, Van Beylen and Smets 1s7)found that the propagation of styrene also exhibited a square root dependence of rate upon active center concentration when anisole or 4-ethylanisole was present over an ether/lithium range of 33 to 1030, and also in the presence of 2-ethylanisole for the range 40 to 3980. The cross-over reaction between poly(styryl)lithium and "double diphenylethylenes" in benzene with diphenyl ether (ether lithium of 150) also showed a one-half order dependence on active center concentration ~ss) The influence of tetrahydrofuran, diphenyl ether and anisole on the association of poly(styryl)lithium active centers in benzene solution has been examined 42, 52) by the viscometric technique.

Crassous et al. 177) studied the polymerization of ethylene using n-butyllithium in conjunction with the tertiary diamines TMEDA, TEEDA (tetraethylethylenediamine) and PMDT (pentamethyldiethylenetriamine). In contrast to the situation with TMEDA the rate of polymerization was found to show a first order dependence upon the complexed chain end concentration. Steric hindrance seems to prevent the dimerization of the chain ends. Examination of the n-BuLi. TEEDA complex by 1H-NMR shows that the displacement to high field of the protons ~ to the lithium induced by complexation is much smaller with TEEDA than with TMEDA or PMDT.

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