CRYOOZONOLYSIS OF SOME PERFLUOROOLEFINS
1743
We also examined the possibility of initiating poly-
merization of monomers containing no fluorine. Ozo-
nide II effectively initiates polymerization of liquid
methyl methacrylate (MMA) and acrylonitrile (AN)
at room temperature. Figure 4 shows kinetic curves
of MMA polymerization at room temperature and
various initial concentrations of ozonide II. The result-
ing polymer is insoluble in methyl ethyl ketone, which
is untypical of polymethyl methacrylate. A chemical
analysis showed incorporation of fluorine into the
macromolecule in amounts significantly exceeding the
content corresponding to addition of the initiator frag-
ment in the initiation stage. Presumably, in the course
of MMA polymerization, the decomposition products
of the initiator or perfluoro-4-methyl-2-pentene are
incorporated in the macromolecule. Preparation of
polymethyl methacrylate containing perfluoro groups
is also of practical interest.
(3) Polymerization of methyl methacrylate initi-
ated with ozonide yields a polymer containing per-
fluoro groups.
ACKNOWLEDGMENTS
The study was supported by the Russian Founda-
tion for Basic Research, project no. 00-03-32212.
REFERENCES
1. Ismoilov, I.L., Atakulov, Sh.B., Muidinov, M.R.,
et al., Dokl. Akad. Nauk SSSR, 1987, vol. 295, no. 5,
pp. 1159 1163.
2. Ismoilov, I.L., Kiryukhin, D.P., Barkalov, I.M., et al.,
Khim. Fiz., 1989, vol. 8, no. 1, pp. 98 101.
3. Kiryukhin, D.P., Ismoilov, I.L., and Barkalov, I.M.,
Low-Temperature Ozonolysis of Fluoroolefins, Pre-
print of the Division of the Institute of Chemical
Physics, USSR Acad. Sci., 1988.
Thus, ozonide II can be used as initiator for poly-
merization of various monomers; in contrast to usual
initiators, it does not require use of elevated tempera-
tures.
4. Kiryukhin, D.P., Barkalov, I.M., and Ismoilov, I.L.,
Zh. Prikl. Khim., 2001, vol. 74, no. 4, pp. 682 683.
5. Barkalov, I.M. and Kiryukhin, D.P., Int. Rev. Phys.
Chim., 1994, vol. 13, no. 2, pp. 337 357.
6. Nielsen, A.A., Burke, T.G., Woltz, P.I., and Jones, E.A.,
CONCLUSIONS
J. Chem. Phys., 1952, vol. 20, no. 3, pp. 596 604.
7. Razumovskii, S.D. and Zaikov, G.E., Ozon i ego re-
aktsii s organicheskimi soedineniyami (Ozone and Its
Reactions with Organic Compounds), Moscow: Na-
uka, 1974.
(1) Low-temperature ozonolysis of perfluoro-4-
methyl-2-pentene involves addition of ozone across
the double bond in equimolar ratio; cryoozonolysis
of perfluoro-2,4-dimethyl-3-ethyl-2-pentene does not
occur under these conditions.
8. Criegee, R., Angew. Chem. Int. Ed., 1975, vol. 14,
no. 21, pp. 596 604.
9. Cremer, D., J. Am. Chem. Soc., 1981, vol. 103,
(2) Perfluoro-4-methyl-2-pentene ozonide is stable
at room temperature and can effectively initiate poly-
merization of commercial perfluoroolefins, methyl
methacrylate, and acrylonitrile.
no. 13, pp. 3633 3688.
10. Panshin, Yu.A., Malkevich, S.G., and Dunaev-
skaya, Ts.G., Ftoroplasty (Fluoroplastics), Leningrad:
Khimiya, 1978.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 74 No. 10 2001