Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 2, pp. 329−333.
Pleiades Publishing, Ltd., 2011.
Original Russian Text © G.A. Emel’yanov, V.M. Rodin, D.P. Blinov, V.V. Berenblit, 2011, published in Zhurnal Prikladnoi Khimii, 2011, Vol. 84, No. 2,
Telomerization of Perﬂ uoropoly(oxamethylene iodides)
with Triﬂ uoroethylene
G. A. Emel’yanov, V. M. Rodin, D. P. Blinov, and V. V. Berenblit
Lebedev Research Institute of Synthetic Rubber, Federal State Unitary Enterprise, St. Petersburg, Russia
Received April 29, 2010
Abstract—Radical telomerization of perﬂ uoropoly(oxamethylene iodides) with triﬂ uoroethylene was studied.
Based on the
F NMR spectroscopic data, the pathways for oleﬁ n addition to the iodide in the initial and
subsequent stages were examined.
Radical telomerization of ﬂ uorooleﬁ ns, in particular,
of tetraﬂ uoroethylene and triﬂ uorochloroethylene,
with perhalogenated telogens has been known
since the middle of the XX century . This is an
efﬁ cient way to prepare semiproducts for synthesis
of monomers, vulcanizing agents, and precursors
of modiﬁ cation of nanomaterials, as well as other
useful products. Ankudinov et al. reported on
telomerization of triﬂ uoroethylene with 1,2-dichloro-
4-iodoperﬂ uorobutane, in which 5-hydro-1,2-dichloro-
6-iodoperﬂ uorohexane was obtained in 44% yield .
However, depending on the route of the radical attack
on triﬂ uoroethylene by telogen, telomerization may lead
to isomeric structures differing in the position, geminal
or vicinal, of the proton and iodine.
Here, we examined the structure of isomeric
monoadducts formed from the reaction of perﬂ uoropoly-
(oxamethylene iodides) with triﬂ uoroethylene, initiated
by thermal decomposition of benzoyl peroxide, and the
different routes of formation of the adducts:
The initial iodides were prepared by treatment with
potassium iodide at 200°С of perﬂ uoropoly(oxamethylene
carbonyl chlorides) obtained from carbonyl diﬂ uoride
–СОF yielded by thermal
oxidation of hexaﬂ uoropropene .
Triﬂ uoroethylene was prepared by dehalogenation of
Freon 123B1 (2-bromo-2-chloro-1,1,1-triﬂ uoroethane)
with zinc in isopropanol by a procedure similar to
that described in . Benzoyl peroxide was puriﬁ ed
by reprecipitation from a chloroform solution with
The synthesized products were analyzed by gas-
liquid chromatography on an LKhM-80 chromatograph
(thermal-conductivity detector; temperature-program-