By L. J. Ferry
This exhaustive reference textual content systematically introduces the elemental theories and experimental equipment of anionic polymerization in addition to the synthesis, research, and features of anionically polymerized items.
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The effect, if such a mechanism exists, would be to cause a drop in viscosity. In the present case, the reduction in the mean lifetime of a dimeric aggregate could arise from the 40 R . N . Young, R. P. Quirk and L. J. 0 0 Fig. 11. Influence of TMEDA on the association of the poly(butadienyl)lithium active center. (Reprinted with permission from Ref. 0 Ib@ exchange reaction; (RLi)z + R ' L i • T M E D A ~ ( R L i • R ' L i ) + R L i • T M E D A (40) o n the premise that t w o m o l e c u l e s o f T M E D A c o m p l e x and dissociate one dimer.
Clearly, there is a need for further work, experimental and theoretical, on this topic. 8 Polymerization in the Presence of Tertiary Aminees Since the linear lithium alkyls can be regarded as living oligomers of ethylene, it might be supposed that these would propagate under suitable conditions. An early study by Ziegter and Gellert showed 167) that when propyllithium reacts in ether with ethylene overnight and is subsequently treated with formaldehyde, a mixture of C6, C8, C10 and C12 alcohols is obtained.
In these last two cases, the process of initiation converts the very reactive secondary and tertiary carbanions into the primary ion. A similar phenomenon has been reported by Bartlett et al. lv~) who found that ipropyllithium in ether solution at --60 ° adds only a single molecule of ethylene. Crassous et al. 177) studied the polymerization of ethylene using n-butyllithium in conjunction with the tertiary diamines TMEDA, TEEDA (tetraethylethylenediamine) and PMDT (pentamethyldiethylenetriamine).
Anionic Polymerization by L. J. Ferry