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

Monomer Sequence Control via Living Anionic Copolymerization: Synthesis of Alternating, Statistical, and Telechelic Copolymers and Sequence Analysis by MALDI ToF Mass Spectrometry

“…However, the analysis provided in this previously reported work to support claims that reactivity ratios can be exploited to exclude the DPE monomer from the copolymerization enabling a one-pot, selective, end-capping reaction with the functional DPE is rather qualitative . Summers et al also used amino derivatives of DPE to prepare a variety of telechelic copolymers by ATRP using stoichiometric amounts and sequential addition of the DPE derivative. − Telechelic copolymers with carboxylic acid groups at each chain end were also synthesized by Summers by both ATRP using 4,5-dihydro-4,4-dimethyl-2-[4-(1-phenylethenyl)phenyl]oxazole and by living anionic polymerization using N,N -diisopropyl-4-(1-phenylethenyl)benzamide and deprotection of the carboxylic acid groups postpolymerization. Similarly, DPE derivatives have been used to add phenol groups at the chain terminus by both ATRP and by living anionic polymerization or at the interface between two styrene blocks by living anionic polymerization .…”

Prognostic and therapeutic impact of the chromosome 20q13.2 ZNF217 locus amplification in ovarian clear cell carcinoma

“…The first approach is to use a designed functional initiator, wherein functional group is tolerant to ATRP reaction conditions which results in the formation of α‐functionalized polymers. Polymers with α‐ as well as α‐,α′‐homobifunctional groups such as dihydroxyl,14, 15 dicarboxylic acid,16 bis(4‐fluorobenzoyl),17 bis(aromatic bromo),18 and tert ‐amino19 have been prepared successfully using initiator approach. The second approach is to transform the halogen end group of the polymer into different useful functional groups by post‐polymerization modification.…”

Cuso4 -amine redox-initiated radical polymerization of methyl methacrylate mediated by a CuCl2 complex: Homogeneous reverse ATRP

“…Summers performed Cu I /L‐catalyzed atom transfer radical addition (ATRA) of 1‐bromoethylbenzene to 1‐(4‐dimethylaminophenyl)‐1‐phenylethylene or 1,1‐ bis [(4‐dimethylamino)‐phenyl]ethylene as a functional monomer, giving rise to the corresponding mono‐adduct of both a C‐X moiety and 4‐dimethylaminophenyl moieties. Followed by addition of St, these monoadducts in situ initiate ATRP to prepare alpha‐amino PSt . As a prototype to redox‐initiated homogenous reverse ATRP, the protocol we formulated here provides a facile approach to alpha‐amino polymers directly from commercially available tertiary amines such as TEA.…”