Tertiary amine‐functionalized polymers by atom transfer radical polymerization

Abstract

The quantitative synthesis of tertiary amine‐functionalized polymers by atom transfer radical polymerization is reported. Tertiary amine‐functionalized polystyrene was prepared with the adduct of 1‐(bromoethyl)benzene with 1‐(4‐dimethyl‐aminophenyl)‐1‐phenylethylene as an initiator in the atom transfer radical polymerization of styrene in the presence of a copper (I) bromide/2,2′‐bipyridyl catalyst system. The polymerization proceeded via a controlled free‐radical polymerization process to afford quantitative yields of the corresponding tertiary amine‐functionalized polystyrene with predictable number‐average molecular weights (1600–4400), narrow molecular weight distributions (1.09–1.31), and an initiator efficiency of 0.95. The polymerization process was monitored by gas chromatographic analysis. The tertiary amine‐functionalized polymers were characterized by thin‐layer chromatography, size exclusion chromatography, potentiometry, and spectroscopy. All experimental evidence was consistent with quantitative functionalization via the 1,1‐diphenylethylene derivative. Polymerization kinetic measurements showed that the polymerization reaction followed first‐order‐rate kinetics with respect to monomer consumption and that the number‐average molecular weight increased linearly with monomer conversion. © 2001 John Wiley & Sons, Inc. J Polym Sci A Part A: Polym Chem 39: 2058–2067, 2001

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

“…The ATRP of styrene initiated by 4‐(dimethylamino)benzyl 4‐bromomethylbenzoate affords well defined α‐tertiary amine functionalized polymers with narrow molecular weight distributions. Furthermore, by using 1,1‐diphenylethylene chemistry methods, a new quantitative ATRP functionalization method for the preparation of tertiary amine functionalized polymers was developed in our laboratories 35, 36. Using a tertiary amine functionalized initiator adduct as the initiator for the polymerization of styrene by ATRP methods, well defined tertiary amine functionalized polymers with good control of M n , M w / M n and chain end functionality were produced.…”

The preparation of α‐bis and α,ω‐tetrakis aromatic oxazolyl‐ and carboxyl‐functionalized polymers using 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene in atom transfer radical polymerization reactions

“…The synthesis of 3 by ATRP methods and the polymerization kinetic studies were effected using the general experimental procedures outlined by Matyjaszewski and co‐workers and Summers and co‐workers . In a typical procedure, under an argon atmosphere, a Schlenk flask was charged with copper (I) bromide (0.0599 g, 0.4177 mmol), bpy (0.1958 g, 1.254 mmol), 1 (0.1564 g, 0.4177 mmol), (1‐bromoethyl)benzene (0.0773 g, 0.4177 mmol) and freshly distilled xylene (1 mL).…”

“…In a separate experiment, the synthesis of 4 was effected by the in situ post‐ATRP chain‐end‐functionalization reaction of 3 with 1 , without the isolation and purification of the functionalized polymeric precursor according to the experimental procedures outlined by Summers and co‐workers . Under an argon atmosphere, precursor 3 was prepared by a typical ATRP procedure using a Schlenk flask charged with the following: copper (I) bromide (0.0477 g, 0.3325 mmol), bpy (0.1558 g, 0.9976 mmol), 1 (0.1245 g, 0.3325 mmol), (1‐bromoethyl)benzene (0.0615 g, 0.3323 mmol) and xylene (1 mL).…”

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

“…Followed by addition of St, these monoadducts in situ initiate ATRP to prepare alphaamino PSt. 108,109 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.…”