ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 1, pp. 82−88. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © G.G. Chernyavskii, G.A. Emel’yanov, V.I. Purtseladze, L.V. Osetrova, 2015, published in Zhurnal Prikladnoi Khimii, 2015, Vol. 88, No. 1,
Copolymers of Vinylidene Fluoride, Hexaﬂ uoropropylene,
and Perﬂ uoroallyl Fluorosulfate
G. G. Chernyavskii, G. A. Emel’yanov, V. I. Purtseladze, and L. V. Osetrova
Lebedev Synthetic Rubber Research Institute, Gapsal’skaya ul. 1, St. Petersburg, 198035 Russia
Received December 31, 2014
Abstract—Radical copolymerization of vinylidene ﬂ uoride (1,1-diﬂ uoroethylene), hexaﬂ uoropropylene (hexa-
ﬂ uoropropene-1), and perﬂ uoroallyl ﬂ uorosulfate (ﬂ uorocopolymer C26-FS) was performed in a solution of
1,1,2-triﬂ uoro-2,2,1-trichloroethane in order to create new low-molecular functional ﬂ uorocopolymers for cold
vulcanization. The optimal copolymerization conditions were determined and a relationship was revealed between
the microstructure of the C26-FS ﬂ uorocopolymer and its physicomechanical characteristics.
F NMR spectros-
copy was used to identify the structure and determine the number-average molecular mass and composition of
the synthesized ﬂ uorocopolymers with a ﬂ uorosulfate group. The thermal stability in an inert medium and the
glass transition temperature of S26-SF and the physicomechanical properties of their vulcanizates were studied.
It was shown the properties and vulcanization duration of low-molecular functional ﬂ uorocopolymers is affected
by the content of perﬂ uoroallyl sulfate units (f = 2–4) relative to the vinylidene ﬂ uoride and hexaﬂ uoropropylene
units in the polymer chain.
There is demand in various ﬁ elds of technology, such
as aerospace, petrochemical, automobile, and nuclear, for
high-tech ﬂ uoropolymeric materials possessing extremal
properties as regards the resistance to aggressive media
Several promising areas of development of fluo-
ropolymer chemistry can be distinguished: development
of ultra- and nanodispersed powder polymeric materials;
elaboration of methods for application of ﬂ uoropolymeric
materials with the use of their solutions; formation of
complex ﬂ uoropolymeric supramolecular systems, such
as membranes; development of composites with nano-
size nonpolymeric ﬁ llers; and modiﬁ cation by various
methods of the already known ﬂ uoropolymeric materials,
with extension of the variety of functional ﬂ uoropolymers
being of most interest .
Among the most demanded fluororubbers are
fluoroelastomers based on vinylidene fluoride
(1,1-difluoroethane, VDF) and hexafluoropropylene
(hexafluoropropene-1, HFP) known as commercial
products under the names SKF-26 (Russia), Viton
and Fluorel (United States), and Dai-el (Japan). These
materials are distinguished by high heat resistance, oil
and petrol resistance, and stability against oxygen and a
number of other corrosive media .
The production of fluoropolymers in Russia and
abroad is mainly concentrated on manufacture of
macromolecular homo- and copolymers, with the fraction
of low-molecular ﬂ uororubbers suitable for fabrication
of articles capable of prolonged operation in severe
conditions being comparatively small.
Among the requirements imposed on low-molecular
(MM < 100 000 Da) ﬂ uoropolymers, the following should
be noted: possibility of operation at low temperatures;
stability in aggressive media; high heat, oil, petrol, and
atmosphere resistance; and sufﬁ cient stability against
ionizing radiation. Also, materials produced from low-
molecular copolymers should satisfy the elastic-strength
requirements to articles on their basis .
To make ﬂ uoroelastomers based on VDF and HFP
capable of vulcanization, including that under the standard
conditions, it is necessary to introduce into the polymer