Preparation of poly(methyl methacrylate) in the presence of ferrocenyl-containing Fe(II) semi- and clathrochelates

Islamova, Regina M.; Sadykova, G. R.; Monakov, Yu. B.; Voloshin, Ya. Z.; Makarov, I. S.; Bubnov, Yu. N.

doi:10.1134/s1070427209080278

Cited by 4 publications

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“…Introduction of bisferrocenylborate macrobicyclic iron(II) tris(dioximate) 20 and 21 into the methyl methacrylate polymerization initiated with diacyl peroxides made it possible to get a sufficiently high process rate at 30-75°С [87][88][89]. Increasing the clathrochelate concentration from 0.01 to 0.02 mmol/L has accelerated the polymerization, but further increase of the complex content has retarded the process.…”

Section: Methodsmentioning

confidence: 99%

“…A new type of catalysts, ferrocenyl-containing iron(II) semi-and clathrochelates, remarkable for the presence of ferrocenyl fragment (or fragments) in the clathrochelate scaffold 20-29 (Scheme 9) has been suggested in [87][88][89][90][91][92]. The choice of such structure of the complex has been inspired by the presence of highly reactive ferrocenyl group [33,55,63] as well as by the special ligand type, macrocyclic clathrochelate with iron(II) as the central atom.…”

Section: Methodsmentioning

confidence: 99%

“…Oximehydrazonate iron(II) clathrochelates 22 and 23 as well as tris(dioximate) complexes 20 and 21 have been recognized as efficient catalysts/mediators of radical polymerization [89].…”

Section: Methodsmentioning

confidence: 99%

“…This section presents comparative analysis of the effects of certain iron complexes (ferrocenes 1 [33], 7 [61], 8-12 [63], clathrochelates 20-23 [87,89], 24-29 [90], and porphyrinates 30-32 [108][109][110]) on radical polymerization of vinyl monomers (methyl methacrylate and styrene) initiated with two types of initiators (benzoyl peroxide and AIBN).…”

Section: Comparison Of Selected Iron Complexesmentioning

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: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

“…Oximehydrazonate iron(II) clathrochelates 22 and 23 as well as tris(dioximate) complexes 20 and 21 have been recognized as efficient catalysts/mediators of radical polymerization [89].…”

Section: Methodsmentioning

confidence: 99%