On the initial stage of the free-radical polymerizations of styrene and methyl methacrylate in the presence of fullerene C60

Yumagulova, R. Kh.; Кузнецов, С. И.; Diniakhmetova, D. R.; Frizen, A. K.; Крайкин, В. А.; Колесов, С. В.

doi:10.1134/s0023158416030150

Cited by 10 publications

(21 citation statements)

References 21 publications

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“…The first concerns the effect of the fullerene-provoked inhibition of the reaction at its initial stage while the second is related to branched-star liked structures of polymer molecules anchored on fullerene. Studies of the second wave of the activity [17][18][19][20][21] were mainly aimed at elucidating the details of the inhibitionfullerene kinetics, with respect to which a wide range of opinions was observed. The vision of the final stage of the reaction, concerning star formation [22], has been generally accepted until now.…”

Section: Introductionmentioning

confidence: 99%

Virtual Free-Radical Polymerization of Vinyl Monomers in View of Digital Twins

Sheka

2023

Polymers

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The first case of virtual polymerization based on the concept of digital twins (DTs) is presented. The free-radical polymerization of vinyl monomers is considered to be a chain reaction consisting of a set of elementary ones. Those three types, related to the polymerization initiation and propagation as well as to the termination of polymer chain growth, are discussed. Special sets of DTs, whose total number approaches 60, distinguish each reaction type. The calculations are carried out using a semi-empirical version of the unrestricted Hartree–Fock approximation. The main energy and spin-density parameters of the ground state of the DTs are determined. The barrier profiles of two pairs of DTs are calculated, based on which two Evans–Polanyi–Semenov relations, attributed to elementary reactions of type (1) and (2), are constructed. These provide a quite reliable evaluation of the activation energy for the initiation and propagation of the free-radical polymerization of vinyl monomers in all the cases. The decisive role of spins in the formation of the elementary reaction transition states is established.

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Section: Introductionmentioning

confidence: 99%

Virtual Free-Radical Polymerization of Vinyl Monomers in View of Digital Twins

Sheka

2023

Polymers

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“…Of particular interest are the antiradical properties of various nanomaterials, including carbon-based nanostructures such as fullerene C 60 . It was noted that the antiradical properties of fullerene C 60 affect the kinetics of radical polymerization of styrene and methyl methacrylate until the polymerization is completely suppressed [2,3]. The kinetics and stoichiometry of the reaction of fullerene C 70 with ozone were described in [4].…”

Section: Introductionmentioning

confidence: 99%

Mechanism of the Antioxidant Activity and Structure–Activity Relationship of N-Monosubstituted Amino Acid Derivatives of Fullerene С60

et al. 2021

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The kinetic characteristics, mechanisms of activity, and relationship between the antioxidant activity and the molecular and supramolecular structure of fullerene C60 and some of its N-monosubstituted amino acid derivatives have been studied. The introduction of an amino acid substituent in the C60 fullerene molecule led to an increase in its antiradical activity in the free radical oxidation of a water-soluble target (fluorescein). The mechanism of the antioxidant activity of amino acid derivatives of fullerene is not associated with the hydrogen atom transfer, electron donation, or catalysis of peroxide decomposition. It was demonstrated that the structure of the amino acid substituent does not affect the antiradical properties, which are thus determined only by the effective total surface area of the nanoparticles of the fullerene C60 derivatives and increase when their size decreases. This surface can be characterized as nanowalls on which the radical death occurs. A change in the concentration of the compounds in solution does not lead to a change in the relative antiradical activity and hence in the nanoparticle size. The results of this study are important for understanding the biological activity of this group of compounds.

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“…As is known, the C 60 fullerene inhibits radical polymerization processes of numerous monomers. However, experimental and theoretical works [1][2][3][4][5][6][7][8][9] revealed C 60 as a weak inhibitor not capable to slow down noticeably the stage of initiating of the chain growth. Quantum chemical simulations demonstrated that the additions of the initiation radicals (benzoxyl and cyanoisopropyl) to C 60 have higher activation energies and lower exothermicities as compared with their addition to typical monomers, methyl methacrylate (MMA) and styrene (St) [8].…”

Section: Introductionmentioning

confidence: 99%

“…However, experimental and theoretical works [1][2][3][4][5][6][7][8][9] revealed C 60 as a weak inhibitor not capable to slow down noticeably the stage of initiating of the chain growth. Quantum chemical simulations demonstrated that the additions of the initiation radicals (benzoxyl and cyanoisopropyl) to C 60 have higher activation energies and lower exothermicities as compared with their addition to typical monomers, methyl methacrylate (MMA) and styrene (St) [8]. The nature of the C 60 effect on the polymerization kinetics (and, consequently, the structure of the produced fullerene-containing macromolecules) depends on the ratio of the reactivities of growing radicals toward the corresponding monomers and C 60 fullerene.…”

Section: Introductionmentioning

confidence: 99%

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Reactivity of short radicals at the initial stages of radical polymerization of allyl chloride: Chain growth versus addition to fullerene

Diniakhmetova

Yumagulova

Колесов

2021

Int J of Quantum Chemistry

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A quantum-chemical study of the C 60 interaction with various radicals generated from monomers in radical polymerization is significant in the fundamental aspects.However, the interactions between fullerene and radicals formed from allyl monomers has been poorly studied. Using the modern density functional theory methods, we performed quantum-chemical simulation on the C 60 interaction with the radicals arising upon the initial stages of the allyl chloride polymerization. We have found that the addition of growth radicals (with 1-4 monomer units) to C 60 are more favorable than the chain growth reactions. Herewith, the radicals with 2-4 monomer units are most reactive in the addition reaction. Our quantum-chemical findings explain the features of the initial stages of the allyl chloride radical polymerization in the presence of C 60 , namely, the increasing inhibition degree of the radical copolymerization of allyl chloride with methyl methacrylate and increasing induction period of copolymerization with styrene.

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On the initial stage of the free-radical polymerizations of styrene and methyl methacrylate in the presence of fullerene C60

Cited by 10 publications

References 21 publications

Virtual Free-Radical Polymerization of Vinyl Monomers in View of Digital Twins

Virtual Free-Radical Polymerization of Vinyl Monomers in View of Digital Twins

Mechanism of the Antioxidant Activity and Structure–Activity Relationship of N-Monosubstituted Amino Acid Derivatives of Fullerene С60

Reactivity of short radicals at the initial stages of radical polymerization of allyl chloride: Chain growth versus addition to fullerene

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