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 telomerization of tetrafluoroethylene in chlorinated telogens at a constant reactor pressure

The kinetics of the radiation-initiated telomerization of tetrafluoroethylene (TFE) in the solutions of telogens (butyl chloride, chloroform, methylene chloride, and carbon tetrachloride) at a constant monomer pressure in the reactor was studied. In the course of the Γ-irradiation of the reaction mixture, TFE telomers containing repeatedly soluble and insoluble fractions were formed. In chloroform, methylene chloride, and carbon tetrachloride, the rapidly occurring process of the synthesis of insoluble telomer made the main contribution to the total yield of products. For the solutions of TFE in butyl chloride, the rates of formation of soluble and insoluble telomers were almost the same. The average chain length and the thermal stability of the resulting telomers were evaluated.     

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.     

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.     

Copper-induced telomerization of tetrafluoroethylene with fluoroalkyl iodides

In the presence of catalytic amounts of cooper, telomerization of tetrafluoroethylene with fluoroalkyl iodides can be carried out at 80-100°C. As compared with usual high-temperature (∼200 °C) telomerization process, the reaction time required is much shorter.     

Radiation-initiated telomerization of tetrafluoroethylene in acetone at a constant monomer concentration

Kinetics of radiation-initiated polymerization of tetrafluoroethylene in acetone was studied at various initial concentrations (pressures) of the monomer in the reactor, which remain constant in the course of synthesis. Concentrated solutions of tetrafluoroethylene telomers were obtained and their properties were examined.     

Molecular mass distribution of oligomers in products of tetrafluoroethylene radical telomerization

The molecular mass distributions (MMD) of perfluorinated oligomers in products of tetra-fluoroethylene (TFE) radical polymerization in various solvents (telogens) were determined from an analysis of differential thermogravimetric curves and data of gel permeation chromatography and mass spectrometry. Radiolysis of the telogens generates radicals initiating polymer chain growth. The choice of the solvent and TFE concentration makes it possible to obtain oligomers with the controlled average chain length from 4 for 40 CF₂ fragments and specified terminal groups. The polymerization of TFE in THF and propylene oxide affords oligomers with cyclic terminal groups capable of further polymerization due to ring opening. The appearance of two MMD maxima (low-molecular-weight at n ₁ ～6–8 and high-molecular-weight at n ₂ > 10 shifting towards high n with an increase in the TFE concentration) is caused by the formation of colloidal solutions of oligomers.     

Molecular-mass-distribution of oligomers in the products of tetrafluoroethylene telomerization in various solvents

The possibility of using differential thermogravimetry (DTG) for determination of the molecularmass-distribution (MMD) of oligomers in polymerization products has been experimentally and theoretically substantiated. The technique is based on the assumptions that the increase in the boiling temperature of oligomers with the increasing chain length is described by the additivity rule and the shape of DTG curves obeys the equation of mass transfer in the stationary convective flow created by evaporation. The results have been confirmed by gel-permeation chromatography and ¹⁹F NMR data. It has been shown that the chain length of oligomers produced via tetrafluoroethylene (TFE) telomerization in carbon tetrachloride, chloroform, acetone, and ethyl acetate reaches about 20–25 C₂F₄ units at an initial TFE concentration of C ₀ ≈ 0.5 mol/l. The MMD includes a low-molecular-mass component (n ≤ 5) in an amount that decreases with increasing C ₀ and a high-molecular-mass component, whose maximum shifts toward higher values of n with an increase in C ₀. The bimodality of MMD is explained in terms of decrease in the propagation rate constant with the accumulation of long oligomers.     

Mechanism of the initiation of low-temperature radiation telomerization of tetrafluoroethylene in hexafluoroisopropanol

ESR and IR spectroscopy and scanning calorimetry are used to investigate the mechanism of low-temperature radiation telomerization of tetrafluoroethylene (TFE) in hexafluoroisopropanol (HFIP). It is found that the low-temperature telomerization of TFE in HFIP proceeds via an ion-radical mechanism. This process is initiated by the radical anions (CF₃)₂C^·-O^? formed during the deprotonation of OH groups of primary hydroxyl radicals (CF₃)₂C^·-OH exhibiting strong acidic properties. An interpretation of ESR spectra of irradiated HFIP recorded at 230–240 K is proposed with regard to the anisotropy on β-fluorine atoms and estimates of the angles between the corresponding C-F bonds and the axis of the unpaired electron orbital.     

Differential thermogravimetric analysis of the products of radiation-chemical telomerization of tetrafluoroethylene in acetone

Differential thermogravimetric (DTG) curves of the products of radiation-chemical telomerization of tetrafluoroethylene solutions in acetone with concentrations (c) of 0.06 to 2.0 mol/l were measured in the temperature range 20–600°C. The pattern of the DTG curves was determined by evaporation of telomers at c < 0.2 mol/l and their thermal degradation at c > 0.2 mol/l. Acetone-soluble telomers with an average chain length of less than 5 units prevail at c < 0.1 mol/l, whereas telomers with a chain length up to 15 units, which form colloid particles, dominate at higher c values. It was shown by means of atomic-force microscopy that such colloid solutions form coatings composed of submicron-sized particles.     

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.     

Kinetics and mechanism of radiation telomerization of tetrafluoroethylene in hexafluoropropan-2-ol and trifluoroethanol

The kinetics of radiation telomerization of tetrafluoroethylene (TFE) in trifluoroethanol and hexafluoropropan-2-ol (HFIP) has been investigated by method of kinetic calorimetry. The nature of active centers initiating the process of telomerization of tetrafluoroethylene in hexafluoroisopropanol in the temperature range of 77—300 K was investigated by ESR spectroscopy. The molecular structure and properties of the obtained telomeres were studied by IR spectroscopy and TGA.     

Formation of colloid solutions and gels during the radiation-chemical telomerization of tetrafluoroethylene in acetone

The polymerization of tetrafluoroethylene (TFE) is initiated by the radicals generated by the radiolysis of acetone. The oligomer chain length n increases with an increase in the initial monomer concentration C. The transition from the true to the colloid solution at C ≈ 0.07 mol/l takes place at an average telomer chain length of $ \bar n $ \bar n ≈ 5. The transition of the colloid solution into gel is observed at C ≈ 0.30–0.35 mol/l. The acetone/TFE ratio in the centrifugation sediment decreases with an increase in the centrifugal acceleration and C. Its minimal value of ∼4 is attained at C > 2 mol/l when $ \bar n $ \bar n ≈ 12–15. The mean particle diameter in the phase separation region is 0.6–0.8 μm. A scaling model of radical polymerization is proposed to explain the molecular-mass distribution of telomers.     

NMR identification of the terminal groups of the telomers of tetrafluoroethylene with tetrahydrofuran

¹H, ¹³C, and ¹⁹F high-resolution NMR spectra with heteronuclear spin-spin decoupling and without it were recorded for identification of the terminal groups of oligomers obtained by radical polymerization of tetrafluroethylene (TFE) in tetrahydrofuran (THF) solutions. The analysis of the spectra and their comparison with the quantum-chemically calculated spectra of possible polymerization products led to the conclusion that the terminal groups of oligomers are the α radical of THF and the hydrogen atom. The structure of oligomers found in this study opens up an opportunity of synthesizing from them polymers consisting of a flexible main chain with substituents in the form of rigid perfluorinated rods.     

Radiation synthesis of telomers at a constant tetrafluoroethylene concentration in acetone

Radiation-initiated polymerization of tetrafluoroethylene (TFE) in acetone has been carried out in a specially designed reactor, which makes it possible to maintain a constant concentration of the monomer in a solution during synthesis. The features of the telomerization process at different initial concentrations (pressures) of TFE have been studied. Concentrated solutions of telomers have been obtained. The carrying out of the process at different pressures in the reactor makes it possible to obtain telomers differing in molecular mass and thermal resistance.     

Radiation induced terpolymerization of tetrafluoroethylene with propylene and n-butyl vinyl ether in bulk

Terpolymerization of tetrafluoroethylene (TFE) with propylene (P) and n-butyl vinyl ether (NBVE) induced by γ-rays at room temperature at dose rate 5 × 10⁵ rad/h and P/NBVE molar ratio from 49/1 to 10/40 was carried out. An alternating copolymerization between TFE and two α-olefins was found to take place in this system, so that 50 mole % of TFE containing terpolymer is always formed at various monomer compositions. The terpolymer composition can be explained successfully by the treatment by a complex mechanism. The complex reactivity ratios of r_I (TFE–complex) and r_II (TFE-NBVE complex) were calculated to be 0.5 and 0.6, respectively, assuming a complex mechanism. The polymerization rate and molecular weight increase with NBVE concentration in the monomer mixture. Colorless transparent rubber-like polymers were obtained at each monomer composition. The glass transition temperature sharply decreases with NBVE concentration in the terpolymer but the thermal and chemical resistances of the terpolymer slightly decrease. Considering these results together with the mechanical properties it has been concluded that the 45/48/7 terpolymer of TFE/P/NBVE molar ratio is good as a practical elastomer useful at relatively low temperatures.     

Radiation synthesis of tetrafluoroethylene telomers with functional hydroxyl and amino end groups in Freon 113

The kinetics of radiation telomerization of tetrafluoroethylene in Freon 113 with ethanol and ammonia additives have been studied by kinetic calorimetry. Tetrafluoroethylene telomers with terminal hydroxyl and amino groups have been obtained. The molecular structure, properties, and composition of the telomers have been investigated by IR spectroscopy, thermogravimetry, and elemental analysis.     

Radiation synthesis of tetrafluoroethylene telomers in chlorosilanes and their use for modification of aluminoborosilicate glass fabric

The kinetics of radiation-initiated telomerization of tetrafluoroethylene in dichlorodimethylsilane and chlorotrimethylsilane have been studied, and the molecular structure and properties of the telomers have been revealed. It has been shown that the introduction of ~3.5 wt % product telomer into aluminoborosilicate glass fabric gives a fluorinated glass-reinforced polymer material with good hydrophobicity.