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Cyclic peroxides as initiators for the radical polymerization of methyl methacrylate were proposed. The initial rates, initiation rates, and effective activation energies of polymerization initiated by cyclic peroxides and cyclic peroxide-1-pyridyl-2-ferrocene systems were determined. The radical yields to the volume upon the thermal decomposition of cyclic peroxides and their catalytic decomposition in the presence of 1-pyridyl-2-ferrocene were determined. In combination with 1-pyridyl-2-ferrocene cyclic peroxides form efficient initiating systems favoring an increase in the polymerization rate, a decrease in the molecular weights, and an increase in syndiotacticity of the synthesized poly(methyl methacrylate). © 2013 Springer Science+Business Media New York.

Influence of 1-[pyridyl-2]-, 1-[quinolin-2-yl]-, 1-[acridin-9-yl]-, 1-[pyrazin-2-yl]-, and 1-[pyrimid-4-yl]ferrocenes on heat and thermomechanical properties of the produced poly(methyl methacrylate) has been studied.

The free-radical bulk homopolymerization of methyl methacrylate and styrene initiated by benzoyl peroxide or AIBN in the presence of heterocyclic derivatives of ferrocene is studied. It is shown that, in the case of the peroxide initiator, ferrocene derivatives form highly efficient initiation systems, which make it possible to polymerize methyl methacrylate at a high rate, to reduce the molecular mass of polymers, and to synthesize polymers with a high content of syndiotactic triads, while in the case of AIBN, such systems are not formed.

The effect of ferrocenyl-containing semi- and clathrochelates on radical polymerization of methyl methacrylate, initiated by benzoyl peroxide, and on molecular characteristics of the polymer formed was examined.

Benzoyl peroxide-, lauryl peroxide-, and AIBN-initiated free-radical polymerization of methyl methacrylate has been studied in bulk and solution in the presence of macrobicyclic iron(II) bis(ferrocenyl borate) tris(nioximate). It has been found that the ferrocenyl-containing iron(II) clathrochelate forms efficient initiating systems with peroxides, whereas, in the case of AIBN, its presence has no effect on the kinetic parameters of the process and the properties of the resulting polymer. The use of clathrochelate complex-peroxide initiator systems accelerates the polymerization of methyl methacrylate and decreases the molecular mass of the polymer. The kinetic parameters of the process have been determined.

Radical polymerization of methyl methacrylate initiated by the benzoyl peroxide — macrobicyclic bis-ferrocenylboron-capped iron(ii) tris-1,2-cyclohexanedione dioximate system was studied. The ferrocenyl-containing macrobicyclic complex and benzoyl peroxide forms an efficient initiating system that allows one to perform the polymerization process at a high rate with substantially reduced amounts of the initiator and the metal complex component at 30–75 °C and to influence the molecular-weight characteristics of poly(methyl methacrylate) produced.

The free-radical polymerization of methyl methacrylate in the presence of chlorine-containing complexes of Fe(III) with 5,10,15,20-tetrakis(3′,5′-di-tert-butylphenyl)porphyrin and 5,10,15,20-tetrakis(3′-butoxyphenyl)porphyrin, as well as in the presence of the acetate complex of Co(III) 5,10,15,20-tetrakis(3′,5′-di-tert-butylphenyl)porphyrin, has been investigated. The kinetic features of the process and the molecular mass characteristics of polymers are studied, and a feasible polymerization mechanism is proposed.

Radical polymerization of methyl methacrylate and styrene initiated by azo-bis-isobutironitrile or benzoyl peroxide in the presence of chlorine-containing complexes of FeIII with 5,10,15,20-tetrakis-(3’,5’-di-tert-butylphenyl)porphyrin, 5,10,15,20-tetrakis-(3’-butoxyphenyl)porphyrin or 5,15-bis(4’-tert-butylphenyl)-2,8,12,18-tetra(n-butyl)-3,7,13,17tetramethylporphyrin and acetate complexes of CoIII with 5,10,15,20-tetrakis-(3’,5’-di-tert-butylphenyl)porphyrin or 5,10,15,20-tetrakis-(3’-butoxyphenyl)porphyrin and complex of CoII with 5,15-bis(4’-tert-butylphenyl)-2,8,12,18tetra(n-butyl)-3,7,13,17-tetramethylporphyrin were investigated. The kinetic features of the process and molecular mass characteristics of polymers were studied. Feasible polymerization scheme was proposed.

The effect of ternary initiating systems benzoyl peroxide-ferrocene-3,6-bis(o-carboxybenzoyl)-N-isopropylcarbazole and benzoyl peroxide-di-η5-indenylzirconium dichloride-3,6-bis(o-carboxybenzoyl)-N-isopropylcarbazole on the radical polymerization of methyl methacrylate and on the heat resistance and microstructure of the resulting polymers was examined.

The radical copolymerization of methyl pheophorbide A with styrene or methyl methacrylate in bulk or in benzene solution initiated by azobisisobutyronitrile at 60–90 °C was performed and kinetically characterized.

The role of the ferrocenium radical cation and Cp2Fe+–O radical in the initiation of methyl methacrylate polymerization in the absence and presence of oxygen was demonstrated.

The pivalate complexes of metals used in the radical polymerization of methyl methacrylate increase rate of process initiated by both benzoyl peroxide and azobisisobutyronitrile and decrease the molecular weight of the resulting polymethyl methacrylate.

Controlled radical polymerization of methyl methacrylate and styrene initiated by azobisisobutironitrile or benzoyl peroxide in the presence of a chlorine-containing complex of Fe III with 5,15-bis(4 ’ - tert -butylphenyl)-2,8,12,18-tetra( n -butyl)-3,7,13,17-tetramethylporphyrin was investigated.

The controlled radical polymerization of methyl methacrylate initiated by the ferrocene–zirconocene dichloride–benzoyl peroxide system was found to occur as a living radical process with an increased concentration of sindio-triads in the resulting poly(methyl methacrylate).