Effect of dicyclopentadiene-and diindenezirconocene dichlorides on free-radical polymerization of methyl methacrylate

Islamova, Regina M.; Puzin, Yu. I.; Yumagulova, R. Kh.; Фатыхов, А. А.; Parfenova, Lyudmila V.; Джемилев, У. М.; Monakov, Yu. B.

doi:10.1134/s0965545x06070078

Cited by 10 publications

(9 citation statements)

References 6 publications

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“…Cl methyl methacrylate complexes has been confirmed by the data of electron absorption, IR, and 1 H NMR spectroscopy [24,42]. A weak coordination bond is formed between the transition metal atom and the oxygen atom of the carbonyl group, affecting the mechanism of the monomer addition to the macroradical.…”

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confidence: 75%

“…The "stereospecific radical polymerization" term has been suggested by the Japanese scientists to describe such processes [20,21]. However, in view of the recently reported data on the effects of structurally diverse metal-containing compounds on the radical polymerization with the character of stereoregular, complex-, and/or coordination-radical behavior [8,17,18,[22][23][24], such processes rather should be regarded as metal-complex radical polymerization, since these processes are based on the complex formation between the metal compound with the macroradical and/or monomer, resulting in the polymer chain propagation vie the cyclic reaction complex [17,18].…”

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confidence: 99%

“…The improved stereoregularity has been observed when other catalytic/ initiating systems are used, in particular, these containing titanocene (2), zirconocene (3), hafnocene (4), and diindenylzirconocene (5) dichlorides (Scheme 3) [23,24,36,38,42,43]. The formation of the 2-methyl methacrylate [23], 3-methyl methacrylate [24], and 5-Mt = Ti (2), Zr (3), Hf (4). …”

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confidence: 99%

“…The detailed studies of the metallocenes effect on the radical polymerization have been reported in [22][23][24][30][31][32][33][34][35][36][37][38][39][40][41][42][43], the considered metallocenes including complexes of iron [22, 23, 30-35, 39, 43], titanium [23, 36-38, 40, 41], zirconium [24,38,42,43], molybdenum [44,45], cobalt [46], ruthenium [47,48], etc.…”

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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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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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“…In addition, the content of 1 in the polymerization system is by one two orders of magnitude smaller as compared with other com pounds (such as Lewis acids, organoelement compounds, and metallocenes) that are used as components of the initiating systems in the radical polymerization of vinyl monomers. 2,3, 8 Since the molecule of 1 contains two ferrocenyl sub stituents, the comparison of the effects of 1 and ferrocene seemed reasonable. As is seen from Fig.…”

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confidence: 98%

Ferrocenyl-containing iron(ii) clathrochelate-benzoyl peroxide, a new initiating system for radical polymerization of methyl methacrylate

et al. 2009

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Radical polymerization of methyl methacrylate initiated by the benzoyl peroxidemacrobicyclic bis ferrocenylboron capped iron(II) tris 1,2 cyclohexanedione dioximate sys tem 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 °С and to influence the molecular weight characteristics of poly(methyl methacry late) produced.

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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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Effect of dicyclopentadiene-and diindenezirconocene dichlorides on free-radical polymerization of methyl methacrylate

Cited by 10 publications

References 6 publications

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

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

Ferrocenyl-containing iron(ii) clathrochelate-benzoyl peroxide, a new initiating system for radical polymerization of methyl methacrylate

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

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