Anionic polymerization hydrocarbon-amine

Effect of Tertiary Amines.—Though the influence of ethereal solvents and additives in anionic polymerizations has been widely investigated, it is only relatively recently that attention has been focussed on the effect of tertiary amines. The complex between Bu"Li and tetramethylethylene diamine (TMEDA) is known to be a powerful base readily capable, for example, of abstracting a proton from aromatic hydrocarbons and generating lithiated derivatives. Not surprisingly, therefore, tertiary amines do indeed have significant effects in carboanionic propagations. 

Also, addition of small quantities of Lewis bases such as amines to alkyllithium reagents in hydrocarbons markedly affects reactivity, especially in connection with various anionic polymerization reactions. Findings such as these prompted a number of research groups in the early 1950 s to study in detail the role of Lewis bases in the structures of organolithium compounds (4, 5). In each case it was concluded that coordination complexes form when amines are added to organolithium reagents in hydrocarbons. 

Anionic polymerization is caused by compounds that give rise to anions in the reaction mass. The compounds normally employed to initiate anionic polymerization are Lewis bases (e.g., primary amines or phosphenes), alkali metals (in the form of suspensions in hydrocarbons), or some organometallic... 

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