Effect of a three-component initiation system ferrocene-zirconocene dichloride-benzoyl peroxide on the free-radical polymerization of methyl methacrylate

Islamova, Regina M.; Sadykova, G. R.; Puzin, Yu. I.; Спирихин, Л. В.; Крайкин, В. А.; Monakov, Yu. B.

doi:10.1134/s1560090408050060

Cited by 7 publications

(6 citation statements)

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“…However, the polydispersity index of the product prepared in the presence of the discussed complexes cannot be significantly decreased. In this regard, the systems based on chlorinated iron porphyrinates and AIBN [109][110][111] as well as bimetallocene catalytic/initiating systems [68][69][70][71] are promising, inducing the "living" process during polymerization of methyl methacrylate and styrene.…”

Section: Influence On Propagation and Chain Terminationmentioning

confidence: 99%

“…Besides the combinations of metallocenes and nitrogen-containing compounds, catalytic/initiating systems based on a pair of metallocenes have been developed [67][68][69][70][71]. The introduction of a pair of compounds of the same class into the polymerization system was expected to result in their additive effect, as observed in the case of combining compounds 2-3 or 3-4 with organic peroxide.…”

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confidence: 99%

“…It has been anticipated that the combination of metallocene 1-5 and compound 6 in the catalytic/initiating system may preserve the stereo control simultaneously accelerating the polymerization. However, the investigation of polymerization of methyl methacrylate initiated by the three-component systems has shown that metallocene has the major effect on kinetic parameters of the polymerization and properties of the prepared polymer (see the table) [43,55,[57][58][59][60].…”

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confidence: 99%

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Iron compounds in controlled radical polymerization: Ferrocenes, (clathro)chelates, and porphyrins

Islamova

2016

Russ J Gen Chem

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Abstract-Experimental data on the application of metal complexes in radical polymerization of vinyl monomers collected over the recent 15 years have been analyzed and generalized. Special attention has been given to (un)substituted ferrocenes, macrocyclic (clathro)chelates, and iron porphyrinates as well as to the approaches to enhance their catalytic activity in controlled synthesis of macromolecules. The mentioned systems have been compared with each other as well as with selected complexes of other transition metals. It has been shown that the electronic and spatial structures of the metal complexes are related to their efficiency in the radical polymerization reactions. Keywords: controlled radical polymerization, metallocene, (clathro)chelate, metal porphyrinate, catalytic/ initiating system Application of metal complexes opens broad prospects to control the polymerization processe and to prepare polymer materials with improved physicochemical properties. The metal complex catalysis has become of special importance in the field of controlled radical polymerization over the recent 15 years.The term "controlled radical polymerization" is generally referred to "living" or "pseudo-living" radical polymerization; its mechanism, irrespectively of the type of the catalysts/mediators applied (metal complexes [1-11], nitroxyl compounds [12-14], thioesters [15,16], etc.) is based on minimization of the probability of the interaction between the propagating radicals, resulting in the irreversible chain termination. This allows for control of molecular parameters of the prepared polymers, in particular, reduction of the polydispersity coefficient down to M w /M n = 1.1, achieving the linear behavior of the number-average molecular mass (M n ) as function of the conversion, elimination of the undesirable gel effect, and preparation of block copolymers.Atom Transfer Radical Polymerization (ATRP) [1], Transition Metal-Catalyzed Living Radical Polymerization [7], and Organometallic Mediated Radical Polymerization (OMRP) [11] are among the types of controlled radical polymerization. The first approach is based on the use of halides of organic complexes of transition metals, leading to the formation of labile terminal carbon-halogen bond (P n -Hlg). Under certain conditions, this bond is capable of dissociation to regenerate the initial or new active radical further propagating the polymer chain (Scheme 1).Here P n · stands for the propagating macroradical, М is the vinyl monomer, HlgMt x+1 /L is the metal complex halide (with L as the organic ligand), Mt is the transition metal, and k p is the rate constant of the chain propagation.The second of the listed methods uses stable radical organometallic species or diamagnetic transition metal complexes forming the carbon-metal bond P n -Mt as the regulators of the polymer chain growth [11] (Scheme 2).Due to the similarity of these two approaches their simultaneous operation is often assumed [11].Besides "living" radical polymerization, complexand/or coordination-radical polymeri...

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Section: Influence On Propagation and Chain Terminationmentioning

confidence: 99%

mentioning

confidence: 99%

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confidence: 99%

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Iron compounds in controlled radical polymerization: Ferrocenes, (clathro)chelates, and porphyrins

Islamova

2016

Russ J Gen Chem

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“…15 The complex formation of ferrocene and BP was studied. 16 It is also known that tertiary aromatic amines are activators of polymerization of vinyl monomers and catalyze the decomposition of peroxide initiators. 17 The study of the systems based on BP and heterocyclic fer rocene derivatives found the synergetic catalytic effect of two groups, metallocene and nitrogen containing, com bined at the molecular level.…”

Section: Resultsmentioning

confidence: 99%

Cyclic peroxides and related initiating systems for radical polymerization of methyl methacrylate

et al. 2013

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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 deter mined. 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).

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“…Complexation of metallocenes (ferrocene, zirconocene dichloride, diindenylzirconocene dichloride and titanocene dichloride) with MMA via coordination of central metal atom of organometal compound with oxygen atom of carbonyl group of monomer was proved by spectral methods. [20][21][22] Apparently considerable deceleration of MMA polymerization in the presence of benzoyl peroxide and iron porphyrin caused by participation of monomer in complexation of initiator and additive, which does not occur in the styrene polymerization under the same conditions. The benzoyl peroxideinitiated polymerization of styrene performed in the presence of iron porphyrin exhibits features of the living process to a greater extent compared to MMA polymerization.…”

Section: (B)];mentioning

confidence: 93%

Influence of 5,15-bis(4’-tert-butylphenyl)-2,8,12,18-tetra(n-butyl)-3,7,13,17-tetramethylporphyrin of FeIII on methyl methacrylate and styrene radical polymerization

Monakov

Islamova

Ионова

et al. 2010

Mendeleev Communications

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Effect of a three-component initiation system ferrocene-zirconocene dichloride-benzoyl peroxide on the free-radical polymerization of methyl methacrylate

Cited by 7 publications

References 2 publications

Iron compounds in controlled radical polymerization: Ferrocenes, (clathro)chelates, and porphyrins

Iron compounds in controlled radical polymerization: Ferrocenes, (clathro)chelates, and porphyrins

Cyclic peroxides and related initiating systems for radical polymerization of methyl methacrylate

Influence of 5,15-bis(4’-tert-butylphenyl)-2,8,12,18-tetra(n-butyl)-3,7,13,17-tetramethylporphyrin of FeIII on methyl methacrylate and styrene radical polymerization

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