Kinetic scheme and rate constants for methyl methacrylate synthesis occurring via the radical–coordination mechanism

Ulitin, N. V.; Tereshchenko, K. A.; Frizen, A. K.; Burakova, A. O.; Колесов, С. В.; Shiyan, D. A.; Темникова, Н. Е.

doi:10.1134/s0023158417020136

Cited by 6 publications

(2 citation statements)

References 28 publications

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“…Based on experimental and theoretical studies of classical radical polymerization, − on experimental studies − of the kinetics of radically initiated polymerization processes in the presence of metallocenes and molecular characteristics of the resulting polymers, as well as studies devoted to theoretical quantum chemical ,− and kinetic − modeling of these processes, it was concluded that two channels of polymer chain formation exist concurrently in the polymerization under consideration, the radical and the coordination channels; therefore, it can be called radical coordination polymerization. During the polymerization of methyl methacrylate in the presence of benzoyl peroxide and ferrocene (compared to the polymerization of methyl methacrylate in the presence of benzoyl peroxide only) the following was found: (1) the molecular weight of the resulting poly(methyl methacrylate) decreases, and at the same time, the average molecular weights of the polymer increases with growing conversion of methyl methacrylate − (which is observed in processes with reversible chain deactivation); (2) the proportion of syndiotactic triads in the composition of poly(methyl methacrylate) increases (which indicates to the course of chain coordination propagation reactions); (3) poly(methyl methacrylate) is obtained, which is capable to act as a macroinitiator with constant activity while adding new portions of a monomer .…”

Section: Introductionmentioning

confidence: 99%

Kinetics of Methyl Methacrylate Polymerization in the Presence of Initiating Systems “Peroxide + Zirconocene Dichloride” When the Methyl Methacrylate Adhesive is Cured

Tereshchenko,

Shiyan,

Osipov

et al. 2024

Ind. Eng. Chem. Res.

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A kinetic model of the curing of methyl methacrylate adhesive (including nanocomposite methyl methacrylate adhesive) in the presence of the initiating systems "aryl peroxide + zirconocene dichloride" and "aryl hydroperoxide + zirconocene dichloride" is made. Computational experiments have been carried out which demonstrate the relationship of the curing rate with the curing temperature in the range of 323−343 K and with the ratio of the initial concentration of zirconocene dichloride to the initial concentration of the initiator [Mc] 0 /[I] 0 for the following initiators: benzoyl peroxide (PB), ethylbenzene hydroperoxide (HPEB), and ethylbenzene hydroperoxide adduct with cadmium 2-ethyl hexanoate [HPEB•Cd(EH) 2 ]. It is shown that in order to increase the curing rate of the adhesive, curing should be carried out at a higher temperature (343 K) and at a higher value of the ratio [Mc] 0 /[I] 0 = 10 in the presence of the most rapidly decomposing initiator HPEB•Cd(EH) 2 . To increase the weight-average molecular weight of poly(methyl methacrylate), the proportion of syndiotactic triads in its composition, and consequently, to improve the adhesion strength and heat resistance of the adhesive joint, the curing of the adhesive must be carried out at the reduced temperature (323 K) and the reduced ratio of the [Mc] 0 /[I] 0 = 0.1 in the presence of the least rapidly decomposing initiator HPEB.

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Section: Introductionmentioning

confidence: 99%

Kinetics of Methyl Methacrylate Polymerization in the Presence of Initiating Systems “Peroxide + Zirconocene Dichloride” When the Methyl Methacrylate Adhesive is Cured

Tereshchenko,

Shiyan,

Osipov

et al. 2024

Ind. Eng. Chem. Res.

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“…On the other hand, the capabilities of modern computational chemistry can be used successfully for this purpose. [7,8] Therefore, in this study were performed a quantum-chemical simulation of the possible pathways in a reaction of an oxotitanium(IV) porphyrin with methyl methacrylate radicals, estimated the energy characteristics of potential reactions, and analyzed the structure of the intermediates.…”

Section: Introductionmentioning

confidence: 99%

The Reactions of Oxotitanium(IV) Tetraphenylporphyrin with Methyl Methacrylate Radicals: A DFT Study

Friesen¹

2018

MHC

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A theoretical analysis of potential reactions between oxotitanium(IV) tetraphenylporphyrin with methyl methacrylate radicals was made. The structures of possible products were calculated and the energies of their formation were estimated. The oxotitanium(IV) tetraphenylporphyrin ((TPP)Ti=O) and the CH 3-CH 2-C • (CH 3)(C(O)OCH 3) radical, which simulated a poly(methyl methacrylate) propagating radical, were used as the model particles for quantumchemical calculations. It has been shown that addition of the radical to the titanium atom does not occur, among other reactions the addition of radical to the O atom (extraligand) is the most likely process. As a result, the metal-centered radical (TPP)Ti •-OR is formed, which can act as a trap for other methyl methacrylate radicals. Such radical addition occurs on the opposite side from the extraligand. In the (TPP)Ti(OR)(R) product, the radical is added to the titanium atom not by the C atom but by the O atom of the carbonyl group. Furthermore, it has been shown that β-H transfer does not occur with participation of the titanium atom belonging to (TPP)Ti=O, but is principally possible with involvement of the extraligand. The β-H transfer involving the titanium atom in (TPP)Ti •-OR is energetically unfavorable.

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About building a basis surface in inverse kinetic problems for non-break processes of diene polymerization

Gizzatova

Ismagilova

Podvalny

2021

J. Phys.: Conf. Ser.

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The work contains a mathematical description of diene polymerization with a neodym-based Ziegler-Natta catalysts. The resulting system of differential equations was reduced from infinite to finite by the method of moments. For this, the basis of nonlinear parametric functions was searched with a method allowing obtain expressions that reflect the kinetics of the polymerization process. The obtained basis of two functions enables us to construct a surface containing local regions of the minimum of the objective function which define the starting points for search of optimum kinetic constant values.

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Kinetic scheme and rate constants for methyl methacrylate synthesis occurring via the radical–coordination mechanism

Cited by 6 publications

References 28 publications

Kinetics of Methyl Methacrylate Polymerization in the Presence of Initiating Systems “Peroxide + Zirconocene Dichloride” When the Methyl Methacrylate Adhesive is Cured

Kinetics of Methyl Methacrylate Polymerization in the Presence of Initiating Systems “Peroxide + Zirconocene Dichloride” When the Methyl Methacrylate Adhesive is Cured

The Reactions of Oxotitanium(IV) Tetraphenylporphyrin with Methyl Methacrylate Radicals: A DFT Study

About building a basis surface in inverse kinetic problems for non-break processes of diene polymerization

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