Radical polymerization of methyl methacrylate in the presence of benzoyl peroxide, ferrocene and zirconocene dichloride

Monakov, Yurii B; Islamova, Regina M.; Frizen, A. K.; Golovochesova, O. I.; Nazarova, Svetlana V.

doi:10.1016/j.mencom.2011.07.012

Cited by 16 publications

(15 citation statements)

References 5 publications

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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%

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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%

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confidence: 99%

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

Islamova

2016

Russ J Gen Chem

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“…The process of methyl methacrylate bulk polymerization runs in the presence of benzoyl peroxide, and ferrocene is characterized by some interactions between the components of the mixture . In addition to the typical reactions for free radical polymerization (initiation, chain propagation, chain termination, and chain transfer), there are also the following interactions between (1) ferrocene and benzoyl peroxide, (2) ferrocene and monomer, and (3) ferrocene and poly(methyl methacrylate) macroradicals; and the reaction of coordination sites formation and chain propagation on these active sites (reactions 1–9, Scheme ; the structures are indicated in a form suitable for further kinetics modeling). However this scheme did not contain the reactions of adduct Ad ( n, z ) with poly(methyl methacrylate) macroradicals and further transformations of the product formed, that is why these reactions were modeled in this work.…”

Section: Resultsmentioning

confidence: 99%

“…The analysis of the experimental facts, the review of polysites of polymerization systems based on the data of molar mass distribution, and the results of quantum chemical modeling of metallocenes interactions with components of polymerization system have led to the conclusion that in radical‐initiated polymerization along with free radicals, the living active sites of the chain propagation are being formed and do function, and on them a coordinating mechanism of monomer addition to the chain is realized being a ligand of the coordination active site …”

Section: Introductionmentioning

confidence: 99%

Modeling of elementary reactions and kinetics of radical‐initiated methyl methacrylate polymerization in the presence of ferrocene

Ulitin

Tereshchenko

Friesen

et al. 2018

Int J of Chemical Kinetics

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On the basis of quantum chemical modeling, a kinetic scheme of methyl methacrylate polymerization initiated by benzoyl peroxide in the presence of ferrocene was proposed. The process runs by mechanism, which includes the reactions of free radical polymerization, and the reactions leading to formation and operability of two type coordination active sites that are capable of converting into each other. On the basis of the proposed scheme, a kinetic model was developed. This model quantitatively described the following: the experimentally determined time dependences of the methyl methacrylate conversion, the conversion dependencies of the numberaverage and weight-average molar masses of poly(methyl methacrylate), the stereoregularity values of poly(methyl methacrylate), and the time dependencies of the methyl methacrylate conversion upon its polymerization on poly(methyl methacrylate) macroinitiators obtained in radical-initiated polymerization in the presence of ferrocene. As a result of solving the inverse kinetic problem, the parameters of temperature dependences of the reaction rate coefficients of the proposed kinetic scheme were found. K E Y W O R D Skinetic model, quantum chemical modeling, radical-initiated methyl methacrylate polymerization in the presence of ferrocene 742

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“…Evidently, the change in the molecular weight charac teristics and stereochemical composition are caused by the influence of the metal complex additive on the chain propagation and termination stages due to the formation of active centers with the growing macroradical, metal locene, and monomer. 19 The coordination of the polymer radical and monomer through the metal atom of the com plexing molecule favors the ordering of monomer addi tion. At the same time, the complex centers formed can not participate in the reactions of square chain termina tion, which makes the termination reaction pseudo mono molecular, most likely, and decreases the MW of the ob tained polymers.…”

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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Radical polymerization of methyl methacrylate in the presence of benzoyl peroxide, ferrocene and zirconocene dichloride

Cited by 16 publications

References 5 publications

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

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

Modeling of elementary reactions and kinetics of radical‐initiated methyl methacrylate polymerization in the presence of ferrocene

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

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