Atom transfer radical polymerization and copolymerization of vinyl acetate catalyzed by copper halide/terpyridine

• Published in: AIChE journal Vol. 55; no. 3; pp. 737 - 746
• Main Authors: Tang, Huadong, Radosz, Maciej, Shen, Youqing
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc., A Wiley Company 01.03.2009; Wiley; American Institute of Chemical Engineers
• Subjects: Applied sciences; atom transfer radical; Catalysis; Catalysts; Catalytic reactions; Chemical engineering; Chemistry; Copolymerization; Copper; Exact sciences and technology; General and physical chemistry; Ions; living radical polymerization; Molecular weight; Organic polymers; Physicochemistry of polymers; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; Reaction kinetics; Reactors; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Catalytic reaction; Polymerization; Copolymerization; living radical polymerization; Hydrolysis; reaction kinetics; First order; Cleavage; Catalysis; Kinetics; Chemical reactivity; Catalyst; atom transfer radical
• ISSN: 0001-1541; 1547-5905
• DOI: 10.1002/aic.11706

Copper-mediated atom transfer radical polymerization (ATRP) is versatile for living polymerizations of a wide range of monomers, but ATRP of vinyl acetate (VAc) remains challenging due to the low homolytic cleavage activity of the carbon-halide bond of the dormant poly(vinyl acetate) (PVAc) chains and the high reactivity of growing PVAc radicals. Therefore, all the reported highly active copper-based catalysts are inactive in ATRP of VAc. Herein, we report the first copper-catalyst mediated ATRP of VAc using CuBr/2,2':6',2"-terpyridine (tPy) or CuCl/tPy as catalysts. The polymerization was a first order reaction with respect to the monomer concentration. The molecular weights of the resulting PVAc linearly increased with the VAc conversion. The living character was further proven by self-chain extension of PVAc. Using polystyrene (PS) as a macroinitiator, a well-defined diblock copolymer PS-b-PVAc was prepared. Hydrolysis of the PS-b-PVAc produced a PS-b-poly(vinyl alcohol) amphiphilic diblock copolymer. © 2009 American Institute of Chemical Engineers AIChE J, 2009