ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 7, pp. 1186−1191. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © A.I. Bol’shakov, S.I. Kuzina, D.P. Kiryukhin, 2015, published in Zhurnal Prikladnoi Khimii, 2015, Vol. 88, No. 7, pp. 1095−1100.
AND POLYMERIC MATERIALS
Radiation-Induced Cotelomerization of Tetraﬂ uoroethylene
with Methyl Acrylate and Tetraﬂ uoroethylene with Acrylamide
in Methylene Chloride Solutions
A. I. Bol’shakov, S. I. Kuzina, and D. P. Kiryukhin
Institute of Problems of Chemical Physics, Russian Academy of Sciences,
pr. Akademika Semenova 1, Chernogolovka, Moscow oblast, 142432 Russia
Received June 30, 2015
Abstract—Kinetics of radiation-induced cotelomerization of tetraﬂ uoroethylene with methyl acrylate and tera-
ﬂ uoroethylene with acrylamide in solutions of methylene chloride was studied. The synthesis process occurs
under the conditions of kinetic chain transfer to the telogen, which involves only the radical with a terminal frag-
ment of tetraﬂ uoroethylene, whereas methyl acrylate or acrylamide molecules are added to the growing telomer
chain. The composition of the telomer and its properties depend on the relative reactivities of the monomers in
the chain-growth reaction. The incorporation of methyl acrylate into the telomer chain results in that the molecu-
lar mass and the fraction of the soluble fraction of the cotelomer become larger. It was found that the adhesion
properties of ﬂ uorine-containing coatings formed on the basis of cotelomers of tetraﬂ uoroethylene and methyl
acrylate are improved.
To obtain low-molecular soluble homologs of Teﬂ on,
studies of the polymerization of tetraﬂ uoroethylene
(TFE) in various solvents (telogens) are carried out.
The formation of a low-molecular polymer in solution
is associated with the chain transfer by a growing
radical to the solvent, which results in that a low-
molecular polymerization, a telomer, is formed, capable
of initiating the formation of a new telomer chain. In
this case, the main role in reducing the molecular mass
belongs to the process of chain transfer to the solvent,
which interrupts the growth of a material chain and
restricts the molecular mass of the telomer. The growth
of the telomer chain is terminated in both early and
late stages of the process, and, therefore, the telomers
obtained have a broad molecular-mass distribution
and contain both soluble and insoluble fractions [1, 2].
Introduction of an additional chain-transfer agent that is
more effective than the telogen results in a substantial
decrease in the molecular mass and formation of a fully
soluble telomerization product .
It is known that an important disadvantage of TFE
telomers is in their weak adhesion, which restricts their ap-
plication as thin protective coatings . The cotelomeriza-
tion of TFE and monomers containing in their composition
polar functional groups improving the adhesive cohesion
with the surface may serve as a way to change the proper-
ties of TFE telomers. These cotelomerization reactions can
also be used for synthesis of necessary ﬂ uorine-containing
compounds and composites on their basis.
Cotelomers are obtained by two methods: joint
cotelomerization of two monomers and the reaction of the
telomer with the second monomer. The radiation-initiated
cotelomerization is poorly understood.
Our study is concerned with the kinetics of radiation-
induced cotelomerization of TFE with methyl acrylate and
TFE with acrylamide in methylene chloride solutions.