Synthesis of a diphenylethylene derivative carrying aromatic tertiary amine groups and its use in chain end functionalization of alkyllithium-initiated polymerizations

Abstract

1,1-Bis[(4-dimethylamino)phenyl]ethylene was successfully synthesized through the ‘Wittigtype’ reaction of 4,4′-bis(dimethylamino)benzophenone with the ‘Tebbe’ reagent. The methylenation yields were over 80 wt.-% on the basis of the initial amount of benzophenone derivative used. Terminally functionalized polymers having aromatic tertiary amine groups at one end or at both ends were prepared by the crossover reactions of n-butyllithium (n-BuLi), poly(styryl)lithium (PSLi), and poly(isoprenyl)lithium (PILi) with the diphenylethylene analogue. The functionalization yields were over 87 mol.-% based on the results of 1H NMR spectroscopic analysis. The number-average molecular weights of the polymers based on the ratio [gram of monomer]/[mole of initiator] are in good accordance with those observed from size exclusion chromatographic and 1H NMR spectroscopic analysis (3,0 × 103 ∼ 7,5 × 103 g/mol).