Polymerization of Coordinated Monomer

If a monomeric metal complex containing a vinyl group is polymerized without side reactions, a polymer-metal complex having uniform structure can be obtained. 

Both typical and exceptional examples of the polymerization of a vinyl monomer containing a transition-metal ion are provided by the radical polymerization of vinylferrocene31. Vinylferrocene and its derivatives are polymerized by a radical or a cationic initiator to form a polymer of high molecular weight. The high polymeriz-ability is based on the property that the ferrocene compounds are extraordinarily stable against chemical reactions. 

It is well known that transition-metal salts and metal complexes, unlike non-Werner-type ferrocene compounds, act as inhibitors in the polymerization of vinyl monomers. For example, the radical polymerization of vinylpyridine is strongly inhibited in the presence of Cu(II) or Fe(III)32 However, vinylpyridine with Cu(I) 

We have reported the radical polymerization of Cu complexes with the Schiff-base ligand containing a vinyl group 2534 The polymer was obtained when the 

Polymerization of the complex monomer is also interesting as a method for controlling the reactivity of the vinyl monomer and the steric configuration of the resulting polymer. Osada35,36) has reported the radical polymerization of methacrylate (MA) monomers coordinated to Co(III) complexes [Co(NH3)(MA)](C104) 2 26 and crs-[Co(NH3)4(MA)2]C104 27. It was found that the complex monomers 26 

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Okazawa, S. Hirai, H. Makishima, S. Polymerization of coordinated monomers. I. Stereoregulation in the free-radical polymerization of methyl methacrylate-zinc chloride or methyl methacrylate-stannic chloride complexes. J. Polym. Set, PartAl Polym. Chem. 1969, 7,1039-1053. 

Bamford C. Alternating copolymerization in the presence of Lewis acids. In Cowie JMG, ed. Alternating Copolymers. New York Springer US 1985 75—152. Hirai H, Takeuchi K, Komiyama M. Polymerization of coordinated monomers. 19. Kinetic study of the alternating copolymerization of methyl-methacrylate with styrene by boron trichloride. J Polym Sci Part A Polym Chem. 1982 20 159-172. 

Hirai H, Tanabe T, Koinuma H. Polymerization of coordinated monomers. 16. Stereoregulation in the alternating co-polymerization of methyl-methacrylate with styrene in the presence of metal halides. J Polym Sci Part A Polym Chem. 1980 18 203-222. Gotoh Y, lihara T, Kanai N, Toshitna N, Hirai H. Synthesis of highly coheterotactic poly(methyl methacrylate-alf-styrene). Chem Lett. 1990 2157—2160. 

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