ISSN 1070-4272, Russian Journal of Applied Chemistry, 2014, Vol. 87, No. 10, pp. 1442−1445. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © A.I. Bol’shakov, S.I. Kuzina, D.P. Kiryukhin, V.M. Buznik, 2014, published in Zhurnal Prikladnoi Khimii, 2014, Vol. 87, No. 10, pp. 1441−1444.
ORGANIC SYNTHESIS AND INDUSTRIAL
Effect of Decanethiol on Radiation-Induced Telomerization
of Tetraﬂ uoroethylene in Chlorinated Solvents
A. I. Bol’shakov, S. I. Kuzina, D. P. Kiryukhin, and V. M. Buznik
Institute of Problems of Chemical Physics, Russian Academy of Sciences,
ul. Akademika Semenova 1, Chernogolovka, Moscow oblast, 142432 Russua
Received June 27, 2014
Abstract—The kinetics of radiation-induced telomerization of tetraﬂ uoroethylene in chlorinated solvents was
studied. In the presence of an additionally introduced chain-transfer agent, 1-decanethiol, the soluble telomers
are formed more efﬁ ciently, and their yield increases. At the ratio tetraﬂ uoroethylene : 1-decanethiol ≤ 2 : 1, the
completely soluble telomer is formed in the system. By varying the reaction mixture composition, it is possible
to control the process and obtain a fully or partially soluble product in a high yield.
Radiation-induced synthesis of tetraﬂ uoroethylene
(TFE) telomers in various solvents (telogens) usually
yields a mixture of soluble and insoluble telomers [1–4].
Their separation requires fractionation of the mixture,
which complicates the production process; furthermore,
at high total yield of the telomerization product (~95%),
the relative amount of the soluble fraction in some cases
does not exceed 5%. Therefore, systems with low yield
of the soluble telomer are unsuitable for developing
an efﬁ cient procedure for preparing soluble telomers.
Low-molecular-mass soluble telomers based on TFE can
ﬁ nd use in preparation of corrosion-protecting coatings,
composite materials, and surfactants; they can also be
used in organic synthesis [5, 6].
The composition of telomers in telomerization
depends on the chain transfer coefﬁ cient С
(i.e., on the
number of chain transfer events), which is the ratio of the
rate constant of chain transfer, K
, to that of the telomer
chain propagation, K
. Therefore, the
telomerization reaction can be optimized by varying the
concentrations of the monomer, chain-transfer agent,
and initiator. In this connection, the use of effective
additional chain-transfer agents altering the composition
and molecular mass of telomers up to the formation of
completely soluble low-molecular-mass reaction products
is of particular importance.
To reduce the molecular mass and enhance the
solubility of telomers formed in radiation-induced
telomerization of TFE in Freon 114В2, we used in 
SH (DT) as an additional chain-
transfer agent. In the pure Freon (without chain-transfer
agent), TFE was virtually fully consumed for the telomer
formation, and already at small irradiation doses (~1 kGy)
the product was an insoluble (~95%) white powder well
competing with commercial Teﬂ on in the heat resistance.
The material chain (depending on the reaction conditions)
consisted of 20–360 units. The solvent, Freon, acted in
this case as the chain-transfer agent. Addition of DT,
which appeared to be a more effective chain-transfer agent
than Freon, to the reaction system allowed the content
of the soluble telomer to be increased, and at the DT
concentration higher than 3 wt % the completely soluble
reaction product was obtained .
Radiation-induced telomerization of TFE in chlorinated
solvents such as chloroform, methylene chloride, and
carbon tetrachloride is similar to that in Freon and also
yields insoluble telomers . The maximal yield (~100%)
was observed at a dose of approximately 17 kGy. The
material chain length in the soluble telomer molecules did
not exceed 10 units; at larger chain length, the telomers
did not dissolve. The formation of telomers of low
molecular mass is associated with efﬁ cient chain transfer