D. P. Kiryukhin

Tetrafluoroethylene telomers: Radiation-initiated chemical synthesis, properties, and application prospects

Systematic studies devoted to the radiation-chemical synthesis of solutions of tetrafluoroethylene telomers in various solvents are summarized. The properties and application prospects of tetrafluoroethylene telomers are considered. Radiation initiation allows new functional products with a broad spectrum of properties to be obtained and new technological approaches with the use of fluorinated polymers to be developed.

Low-temperature radiation chemistry

An overview of studies on the radiation-initiated chemical reactions of polymerization, copolymerization, graft polymerization, telomerization, oxidation, cryoozonolysis, hydrobromination of olefins, and chlorination of paraffins occurring at low and ultralow temperatures has been presented. Particular attention has been paid to self-oscillating reactions.

Radiation Telomerization of Tetrafluoroethylene in Butyl Chloride Solution

The kinetics of the radiation-initiated polymerization of tetrafluoroethylene (TFE) in butyl chloride has been studied. The rate of the process, the properties and yield of telomers obtained depend on the initial concentration of TFE (2.6–22 wt %) in the solution and the dose of γ-irradiation. The analysis of the measured IR absorption spectra and a possible scheme of the process allow to suggest that the main product of the reaction is C4H8Cl(C2F4)n−1CF2CF2H with the formation of small amounts of C4H9(C2F4)n−1CF2CF2H and Cl(C2F4)n−1CF2CF2H. The average number of links in the telomer (n) increases from 7.6 to 16.1 when the concentration of the monomer in the solution varies in the range of 7–22 wt %. The length of the chain of the soluble telomers (n) does not depend on the initial concentration of TFE and makes ∼7.

Radiation-chemical synthesis and properties of tetrafluoroethylene telomeres in fluorine-containing solvents

The kinetics of radiation telomerization of tetrafluoroethylene in a series of fluorine-containing solvents was studied. A comparative analysis of their reactivity was carried out. The structure and some properties of the telomeres were studied by IR spectroscopy, thermogravimetric and elemental analysis, and electron microscopy.

Radiation-initiated telomerization of tetrafluoroethylene in 1,2-dibromotetrafluoroethane

The kinetics of the radiation telomerization of tetrafluoroethylene in 1,2-dibromotetrafluoroethane has been studied. It has been shown that the process occurs very efficiently in the perfluorinated solvent; small doses of γ-radiation (~2 kGy) are required for the complete conversion of the monomer. Telomers with a chain length of 120–360 tetrafluoroethylene units and high thermal stability are formed in the reaction. The structure and properties of the telomers have been studied by IR spectroscopy, thermogravimetry, and elemental analysis.

The Specifics of Radiation Telomerization of Tetrafluoroethylene in Chlorinated Solvents and Telomer Properties

Radiation telomerization of tetrafluoroethylene in butyl chloride, chloroform, and carbon tetrachloride has been investigated. The chain length of telomers and their solubility and thermal stability depend on the initial monomer concentration and telogen properties. In the case of telomerization in chloroform and carbon tetrachloride, the yield, the chain length, and the thermal stability of the telomers are significantly higher than those in butyl chloride, in which the process is less efficient but soluble telomers having a short chain length and exhibiting quite high thermal resistance are produced. The molecular structure of the telomers has been studied by IR spectroscopy.

Spontaneous polymerization of acrylamide in glycerol

The spontaneous polymerization of acrylamide in glycerol in the range of 250–350°C has been first observed and investigated. It has been shown that the polymerization proceeds during dissolution of acrylamide in glycerol and leads to formation of gel globules in which the growth of polymer chains takes place. The reaction occurs without termination of kinetic chains in the living polymerization mode. The effective chain transfer at a low concentration of active centers ensures a high yield of the polymer.

Hydrophobization of polyester textile materials with telomeric tetrafluoroethylene solutions

Hydrophobic coatings formed on a polyester fabric by treatment with telomeric solutions prepared by a radiation-chemical procedure in acetone and butyl chloride were studied by IR spectroscopy (MATIR), energy-dispersive analysis, and atomic force microscopy. The hydrophobic properties of the textile material were evaluated by procedures traditional for textile chemistry. Conditions determining the formation of a thin, highly hydrophobic, uniform, and flawless coating resistant to the effect of operation factors were suggested.

Synthesis and reactivity of metal-containing monomers 72. Monomeric and polymeric metal acetylenecarboxylates and their nanocomposite products: synthesis, structures, and properties

Methods for the synthesis of a number of transition metal acetylenedicarboxylates were developed. The ways and conditions for their polymerization were studied. The polymerization of metal acetylenedicarboxylates was accompanied by the formation of polyconjugated chains. Controlled thermolysis of metal acetylenedicarboxylates yielded matrix-stabilized metal nanoparticles. The microstructures and magnetic properties of the nanocomposites obtained were examined.

Low-temperature radiation telomerization of tetrafluoroethylene in hexafluoroisopropanol

The kinetics of low-temperature (180–270 K) postradiation telomerization of tetrafluoroethylene in hexafluoroisopropanol has been investigated. The efficiency of the process is determined by the initial concentration of the monomer in the solvent and the dose of preliminary irradiation. It has been shown that the telomerization reaction proceeds via the radical mechanism during the devitrification of the system. Active centers that initiate the process and their yield at 77 K have been studied by the ESR technique. Some properties of the product telomers have been studied.