Determination of rate constants for radical telomerization chain growth and transfer from the molecular-mass distribution of oligomer

Kim, I. P.; Benderskiĭ, V. A.

doi:10.1134/s0018143911050080

Cited by 12 publications

(5 citation statements)

References 16 publications

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“…Equations (11) are applicable in dilute solutions at oli gomer concentrations that preclude an overlap of spheres with a diameter L n ; i.e., Since the hydrodynamic sizes of molecules are close to van der Waals sizes, the length of the oligomers in the form of rigid rods is proportional to the number of units:…”

Section: P Kim and V A Benderskiimentioning

confidence: 99%

“…If the temperature is measured in the relative units , only theand parameters remain. Examples of c, T diagrams at different values of the parameters were presented in [11].…”

Section: (37)mentioning

confidence: 99%

“…The model was constructed on the following assumptions substantiated by thermodynamic and quantum chemical calculations [4,5,11]. The highly exothermal chain propagation reactions are diffusion limited, while the chain transfer reactions are ther mally activated kinetic reactions involving the solvent…”

Section: Spatially Inhomogeneous Radical Polymerization Modelmentioning

confidence: 99%

“…In the model of [11], a lattice gas approximation was used, with oligomers depicted by the occupied lattice nodes. The set of N nodes [30] fills the lattice of N 0 nodes with a volume fraction of occupied nodes (34) and the number of possible configurations N 0 !/N!…”

Section: Diagram Of Equilibrium Statesmentioning

confidence: 99%

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Radical polymerization of tetrafluoroethylene that forms a colloid solution and gel of oligomers

Kim

Benderskiĭ

2014

Russ. J. Phys. Chem.

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As the concentration of tetrafluoroethylene (TFE) in the solvent increases, its polymerization is shown to be accompanied by a transformation of the resulting homogeneous solution of oligomers into a col loid one, which then transforms into gel. The micron sized colloid particles consist of oligomers and solvent molecules, whose number per TFE unit in the oligomer decreases from 15-20 at the threshold of dense phase formation to 4-6 in a gel. A kinetic model of polymerization was suggested. In this model, the chain propa gation is limited by monomer diffusion to the growing macroradical and the chain transfer (oligomer forma tion and regeneration of the prime radical) is limited by the reaction of the growing macroradical with the solvent molecule. The model that allows for the decrease in the diffusion coefficients with increasing of the oligomer chain length and their local concentration leads to a spatially inhomogeneous molecular mass dis tribution, with long oligomers accumulated in the vicinity of the macroradical and short ones in the distant zone. The formation of colloid particles and gel occurs when the concentration of long oligomers shaped as rigid rods exceeds the critical value for the dense phase formation and the percolation threshold, respectively. The transition from the initial spatial distribution to the equilibrium distribution described by the phase dia gram was considered using the model of viscoelastic separation so that phases retain spatial continuity.

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Section: P Kim and V A Benderskiimentioning

confidence: 99%

“…If the temperature is measured in the relative units , only theand parameters remain. Examples of c, T diagrams at different values of the parameters were presented in [11].…”

Section: (37)mentioning

confidence: 99%

Section: Spatially Inhomogeneous Radical Polymerization Modelmentioning

confidence: 99%

Section: Diagram Of Equilibrium Statesmentioning

confidence: 99%

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Radical polymerization of tetrafluoroethylene that forms a colloid solution and gel of oligomers

Kim

Benderskiĭ

2014

Russ. J. Phys. Chem.

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“…The propagating radicals react predominantly with pendant double bonds of their own chains to yield microgel particles. This mode of occurrence of the microheterogeneous mechanism of three dimensional radical polymerization can be interpreted within the concepts of nonuniformly spaced radical polymerization [96].…”

Section: Critical Gelation Conversionmentioning

confidence: 99%

Reversible deactivation radical polymerization of polyfunctional monomers

Kurochkin

Grachev

2015

Polym. Sci. Ser. C

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In this review, the results of modern theoretical and experimental investigations of three dimen sional reversible deactivation radical polymerization are discussed. The most important factors affecting the critical gelation conversion, the probability of cyclization, and the topological structures of polymers are underlined. Examples of the most promising application of the reversible deactivation radical polymerization to produce new polymer materials are given.

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Molecular mass distribution of oligomers in products of tetrafluoroethylene radical telomerization

Kim

2013

Russ Chem Bull

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Determination of rate constants for radical telomerization chain growth and transfer from the molecular-mass distribution of oligomer

Cited by 12 publications

References 16 publications

Radical polymerization of tetrafluoroethylene that forms a colloid solution and gel of oligomers

Radical polymerization of tetrafluoroethylene that forms a colloid solution and gel of oligomers

Reversible deactivation radical polymerization of polyfunctional monomers

Molecular mass distribution of oligomers in products of tetrafluoroethylene radical telomerization

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