CuBr2/N,N,N′,N′-Tetra[(2-pyridal)methyl]ethylenediamine/Tertiary Amine as a Highly Active and Versatile Catalyst for Atom-Transfer Radical Polymerization via Activator Generated by Electron Transfer

• Published in: Macromolecular rapid communications. Vol. 27; no. 14; pp. 1127 - 1131
• Main Authors: Tang, Huadong, Radosz, Maciej, Shen, Youqing
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 24.07.2006; WILEY‐VCH Verlag; Wiley
• Subjects: activator generated by electron transfer (AGET); Applied sciences; atom transfer radical polymerization (ATRP); catalyst; Exact sciences and technology; kinetics (polym.); Organic polymers; Physical Sciences; Physicochemistry of polymers; Polymer Science; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; Science & Technology; OXIDATION; MONOMERS; BLOCK-COPOLYMERS; MECHANISM; METHYL-METHACRYLATE; COMPLEXES; atom transfer radical polymerization (ATRP); kinetics (polym.); ATRP; REDUCTION; catalyst; RING-OPENING POLYMERIZATION; activator generated by electron transfer (AGET); ACRYLATES; Bulk polymerization; Atom transfer polymerization; Living polymer; Methyl methacrylate polymer; Electron transfer; Copper complex; Complex catalyst; Experimental study; Methyl acrylate polymer; Pyridine derivatives; Tertiary amine; Reaction mechanism; Styrene polymer; Catalyst activity
• ISSN: 1022-1336; 1521-3927
• DOI: 10.1002/marc.200600258

A highly active and versatile CuBr2/N,N,N′,N′‐tetra[(2‐pyridal)methyl]ethylenediamine (CuBr2/TPEN)‐tertiary amine catalyst system has been developed for atom transfer radical polymerization via activator‐generated‐by‐electron‐transfer (AGET ATRP). The catalyst mediates good control of the AGET ATRPs of methyl acrylate, methyl methacrylate, and styrene at 1 mol‐% catalyst relative to initiator. A mechanism study shows that tertiary amines such as triethylamine reduces the CuBr2/TPEN complex to CuBr/TPEN. The GPC traces of PSt, PMA, and PMMA prepared by AGET ATRP at 1 mol‐% of catalyst relative to initiator are monomodal and have low polydispersities.