α‐Bis and α,ω‐tetrakis(4‐dimethylaminophenyl) functionalized polymers by atom transfer radical polymerization using 1,1‐bis[(4‐dimethylamino)phenyl]ethylene as tertiary diamine initiator precursor and functionalizing agent

Abstract

The quantitative syntheses of α-bis and α,ω-tetrakis tertiary diamine functionalized polymers by atom transfer radical polymerization (ATRP) methods are described. A tertiary diamine functionalized 1,1-diphenylethylene derivative, 1,1-bis[(4-dimethylamino)phenyl]ethylene (1), was evaluated as a unimolecular tertiary diamine functionalized initiator precursor as well as a functionalizing agent in ATRP reactions. The ATRP of styrene, initiated by a new tertiary diamine functionalized initiator adduct (2), affords the corresponding α-bis(4-dimethylaminophenyl) functionalized polystyrene (3). The tertiary diamine functionalized initiator adduct (2) was prepared in situ by the reaction of (1-bromoethyl)benzene with 1,1-bis[(4-dimethylamino)phenyl]ethylene (1) in the presence of a copper (I) bromide/2,2′-bipyridyl catalyst system. The ATRP of styrene proceeded via a controlled free radical polymerization process to afford quantitative yields of the corresponding α-bis(4-dimethylaminophenyl) functionalized polystyrene derivative (3) with predictable number-average molecular weight (Mn) and narrow molecular weight distribution (Mw/Mn) in a high initiator efficiency reaction. The polymerization process was monitored by gas chromatography analysis. Quantitative yields of α,ω-tetrakis(4-dimethylaminophenyl) functionalized polystyrene (4) were obtained by a new post ATRP chain end modification reaction of α-bis(4-dimethylaminophenyl) functionalized polystyrene (3) with excess 1,1-bis[(4-dimethylamino)phenyl]ethylene (1). The tertiary diamine functionalized initiator precursor 1,1-bis[(4-dimethylamino)phenyl]ethylene (1) and the different tertiary amine functionalized polymers were characterized by chromatography, spectroscopy and non-aqueous titration measurements. Copyright © 2012 Society of Chemical Industry