ISSN 1070-4272, Russian Journal of Applied Chemistry, 2007, Vol. 80, No. 3, pp. 386 !388. + Pleiades Publishing, Ltd., 2007.
Original Russian Text + G.F. Myachina, E.N. Sukhomazova, S.A. Korzhova, I.V. Rodionova, E.N. Deryagina, 2007, published in Zhurnal Prikladnoi
Khimii, 2007, Vol. 80, No. 3, pp. 388!390.
AND CORROSION PROTECTION OF METALS
Synthesis and Redox Activity
of Sulfurized Poly(Methylene Polysulfides)
G. F. Myachina, E. N. Sukhomazova, S. A. Korzhova,
I. V. Rodionova, and E. N. Deryagina
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, Russia
Received September 13, 2006
Abstract-Redox-active sulfurized poly(methylene polysulfides) 3[CH
3 (y =4322) were prepared by
deep sulfurization of poly(methylene di- and trisulfides) with elemental sulfur. The use of the substances
obtained as an active cathode material of rechargeable lithium cells ensures their cycling with a specific
discharge capacity of 4183550 mA h g
Sulfur-containing polymers exhibit high electro-
chemical activity and are promising materials for
modern rechargeable chemical power sources .
Their electrochemical behavior is determined by the
presence and number of redox-active S3S bonds in the
structure of these polymers. It is well known that
elemental sulfur can be inserted into S3S bonds of
organic disulfides  and that this process is initiated
by Lewis acids or bases.
Here we report on deep sulfurization of accessible
poly(methylene di- and trisulfides) [7, 8] with elemen-
tal sulfur with the aim to prepare new redox-active
sulfurized poly(methylene polysulfides).
The starting poly(methylene di- and trisulfides)
were prepared by procedures described previously [7,
8]. Their subsequent sulfurization was performed by
heating with elemental sulfur at 1253135oC for 1.5 h.
We examined the effect of a highly basic amine, di-
azabicyclooctane (dabco), of a cobalt salt, CoCl
O, and of their combination on the sulfurization
process and properties of the resulting poly(methylene
3³ 76 ³3CH
x =2,3 y =4322
(y was determined by elemental analysis).
The polymers obtained (nos. 138) were washed
to remove the soluble oligomers and un-
changed sulfur and were vacuum-dried. The reaction
conditions and characteristics of polymers are given
in the table.
We found that, under the reaction conditions, ele-
mental sulfur was actively inserted into the S3S bonds
of the starting poly(methylene di- and trisulfides),
which led to the formation of new polymers enriched
in sulfur to 90398%. The reaction performed without
initiators yielded poly(methylene polysulfides) con-
taining 92.10 and 95.48% S (nos. 1, 5). In the pres-
ence of dabco, the polymer yield increased by 2.9
(no. 2) and 4.3% (no. 6), and the sulfur content in the
sample increased to 94.28 and 98.14%, respectively.
Addition of the cobalt salt (both alone and in combi-
nation with dabco) led to a decrease in the sulfur con-
tent (sample nos. 3, 4, 7, 8; 90.06, 91.65, 94.04, and
The synthesized poly(methylene polysulfides) are
insoluble light brown powders (nos. 1, 2, 4, 5, 6, 8) or
viscous resins (nos. 3, 7). The wide melting interval
of the samples is indicative of their wide molecular-
The IR spectra of the polymers (Specord IR-75 IFS
25 spectrometer, KBr pellets) contain absorption
bands belonging to aliphatic CH
groups: 2922, 2855
); 1511, 1457, 1361, 1176, 1027 cm
the band with a maximum at about 864 cm
cal of the bending vibrations of aliphatic C3H groups
, and the peaks at 7763705 cm
and narrow bands