Enthalpies of formation of radicals and the mass spectra of the products of tetrafluoroethylene polymerization in acetone

Kim, I. P.; Мартыненко, В. М.; Shul’ga, Yu. M.; Shestakov, Alexander F.

doi:10.1134/s0018143910060019

Cited by 8 publications

(4 citation statements)

References 8 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Since reactions (4) occur on the capture sphere, they are described by the conventional differential equations (5) where is the rate constant of chain propagation (increase in the number of macroradical units from to n), which is determined by the monomer flow to the capture sphere;…”

Section: P Kim and V A Benderskiimentioning

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%

“…This contradiction was explained [3][4][5][6] by the presence of intermolecular hydrogen bonds between the terminal groups of oligomers and the solvent mol ecules, which led to the formation of solvation shells of oligomers and their three dimensional framework. This structure of the oligomer solution was confirmed by quantum chemical calculations [4].…”

Section: Introductionmentioning

confidence: 96%

“…It was found [3][4][5][6] that in solvents with more stable CH bonds than in the ter minal H-CF 2 group of the oligomer, the radical poly merization of TFE is accompanied by the formation of a colloid solution, which transforms into gel when the initial TFE concentration increases, leading to oligo mer chain propagation.…”

Section: Introductionmentioning

confidence: 98%

See 3 more Smart Citations

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

Kim

Benderskiĭ

2014

Russ. J. Phys. Chem.

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Section: P Kim and V A Benderskiimentioning

confidence: 99%

Section: Spatially Inhomogeneous Radical Polymerization Modelmentioning

confidence: 99%