Controlled/living radical vinyl acetate

Controlled/ Living radical polymerization (CRP) of vinyl acetate (VAc) via nitroxide-mediated polymerization (NMP), organocobalt-mediated polymerization, iodine degenerative transfer polymerization (DT), reversible radical addition-fragmentation chain transfer polymerization (RAFT), and atom transfer radical polymerization (ATRP) is summarized and compared with the ATRP of VAc catalyzed by copper halide/2,2 6 ,2 -terpyridine. The new copper catalyst provides the first example of ATRP of VAc with clear mechanism and the facile synthesis of poly(vinyl acetate) and its block copolymers. 

KOU 08] Koumura K., Satoh K., Kamigaito M., Manganese-Based controlled/living radical polymerization of vinyl acetate, methyl aciylate, and styrene Highly active, versatile, and photoiesponsive systems , Macromolecules, vol. 41, pp. 7359-7367, 2008. 

KOU 09] Koumura K., Satoh K., Kamig.aito M., Mn2(CO)io-induced controlled/living radical copolymerization of vinyl acetate and methyl aciylate Spontaneous formation of block copolymers consisting of gradient and homopolymer segments , Journal of Polymer Science Part A Polymer Chemistry, vol. 47, pp. 1343-1353, 2009. 

Vinyl acetate (VAc) is one of the most difficult monomers to polymerize in a controlled/living manner. It must be polymerized by a radical mechanism and only a few studies have been reported with well-defined MW and PDI [lOV 03, YAM 04, KOU 08, KOU 08, WAK 01, YAN 10,... 

Substantial effort has been directed toward the control of vinyl acetate (VAc) radical polymerization using living radical polymerization (LRP) methods, including atom transfer radical polymerization, degenerative transfer through alkyl iodide,dialkyl tellurium, trithiocarbonate, xanthate, and cobalt acetylacetonate The focus of... 

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