Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 9, pp. 1623−1625.
Pleiades Publishing, Ltd., 2011.
Original Russian Text © O.G. Lutsenko, O.A. Golubchikov, 2011, published in Zhurnal Prikladnoi Khimii, 2011, Vol. 84, No. 9, pp. 1575−1577.
Synthesis of the Azide Derivative of Cobalt
Tetra(carboxy)phthalocyaninate and its Immobilization
on Nonwoven Polypropylene
O. G. Lutsenko and O. A. Golubchikov
Ivanovo State University of Chemical Engineering, Ivanovo, Russia
Received December 30, 2010
Abstract—Methods of the synthesis of cobalt tetra(carboxy)phthalocyaninate azide derivative and its immobilization
on nonwoven polypropylene and the structure of the phthalocyaninate on a polypropylene ﬁ ber surface were studied.
In last years interest to substituted cobalt(II) phthalo-
cyaninates has considerably grown, which is caused by
their use as effective heterogeneous catalysts of certain
industrially important redox processes, in particular of
the reﬁ nement of petroleum products, sewage, and emis-
Polymeric materials, including polypropylene , are
promising carrying agents of heterogeneous catalysts and
biologically active compounds. Polypropylene is a typi-
cal representative of chemically inert polymeric materi-
als, and its directional surface modiﬁ cation represents
an actual, but at the same time a complicated problem.
Known activation procedures require the use of highly
active reagents, which remain in volume of a polymeric
compound to a varying degree and exert a negative effect
on properties of modiﬁ ed polypropylene.
The aim of the present work was to develop a proce-
dure for obtaining cobalt tetra(carboxy)phthalocyaninate
azide derivative, the synthesis of which allows chemical
immobilizing of a phthalocyanine compound on non-
woven polypropylene without the activation stage of the
polymerous ﬁ ber.
We used analytical-grade o-xylene, a geotextile
nonwoven polypropylene material (GPP) of “Kamenck-
volokno” OJSC production with a density of 400 g m
and a depth of 4 mm. Absorption spectra were recorded
on a U-2000spectrophotometer. IR MFTIR (multiple
frustrated total internal reﬂ ection) spectra were recorded
on an Avatar 360 FT-IR spectrometer.
Cobalt tetra(carboxy)phthalocyaninate chloroan-
hydride. Cobalt tetra(carboxy) phthalocyaninate (1.07 g,
1.42 mmol) was mixed with thionyl chloride (142 ml) in
a ﬂ ask with a reﬂ ux condenser and a stirrer. The mixture
was boiled within 2.5 h at 90°С and then for 2.5 h more
on a boiling water bath up to full dissolution of cobalt
phthalocyaninate. Then the mass was held within one
day at room temperature, and the resulting solution was
poured out in a mixture of distilled water with ice. A pre-
cipitate formed was ﬁ ltered on a glass ﬁ lter and washed
out by an ice solution of sodium chloride up to a neutral
reaction of rinsing water. The product, a powder of dark
green color, is readily soluble in acetone. Yield 0.466 g
(39.5 %). Found (%): C 56.1, H 2.3, Cl 18.3, N 7.2, O 8.5,
Co 7.5. C
Co. Calculated (%): C 56.2, H 2.1,
Cl 18.5, N 7.3, O 8.3, Co 7.7.
Cobalt tetra(carboxy)phthalocyaninate azide de-
rivative. Sodium azide (2.554 g, 39.3 mmol) was added
within 1 h with stirring to a mixture of 40 ml of water
and 0.466 g (0.56 mmol) of cobalt tetra(carboxy)phtha-
locyaninate chloroanhydride cooled up to 0°С. Then the
reaction mixture was held within 1 h at 0°С and further
at 6-8°С up to full dissolution of a precipitate (~12 h).
The product, a powder of blue-green color, is well water-