Sulfonated Co(II) phthalocyanines covalently anchored at organic polymers as catalyst for mild oxidation of mercaptans

Article abstract of DOI:10.1142/S1088424615500911

Current work is devoted to covalent immobilization of sulfonated derivatives of cobalt phthalocyanines "Merox catalysts" on the surfaces of polypropylene and polyethylene terephthalate. Their catalytic activity in reaction of mild oxidation of sulfur compounds to disulfides with oxygen of the air was studied. Anchoring of the catalyst on this polymer prevents its leaching and promotes its efficient recovering and recycling without significant loss of catalytic activity.

Full text of DOI:10.1142/S1088424615500911

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2015; 19: 1–9
DOI: 10.1142/S1088424615500911
Published at http://www.worldscinet.com/jpp/
Sulfonated Co(II) phthalocyanines covalently anchored
at organic polymers as catalyst for mild oxidation
of mercaptans
a◊
a◊◊
a
a
Artur Vashurin* , Ilya Kuzmin , Mikhail Razumov , Svetlana Pukhovskaya ,
b
c◊◊
d
Oleg Golubchikov , Alena Voronina , Gennady Shaposhnikov
and Oscar Koifman
c
a
Department of Inorganic Chemistry, Ivanovo State University of Chemistry and Technology,
Ivanovo 153000, Russia
Department of Organic Chemistry, Ivanovo State University of Chemistry and Technology,
b
Ivanovo 153000, Russia
c
Research Institute of Macroheterocycles of Ivanovo State University of Chemistry and Technology,
Ivanovo 153000, Russia
d
Department of Technology of Fine Organic Synthesis, Ivanovo State University of Chemistry and Technology,
Ivanovo 153000, Russia
Received 7 August 2015
Accepted 20 September 2015
ABSTRACT: Current work is devoted to covalent immobilization of sulfonated derivatives of cobalt
phthalocyanines “Merox catalysts” on the surfaces of polypropylene and polyethylene terephthalate.
Their catalytic activity in reaction of mild oxidation of sulfur compounds to disulfides with oxygen of the
air was studied. Anchoring of the catalyst on this polymer prevents its leaching and promotes its efficient
recovering and recycling without significant loss of catalytic activity.
KEYWORDS: sulfonated Co(II) phthalocyanines, polymer, covalent immobilization, materials,
catalyst, oxidation of mercaptan.
among the many methods of mercaptans removing from
INTRODUCTION
oil fraction — sweetening that includes mercaptans
Oxidation of mercaptans to disulfides is one of the
oxidation in the presence of tetra sulfonic acid of cobalt
main steps of oil sweetening. This process is important for
phthalocyanine [7–10].
petrochemical industry, green chemistry and biochemistry
The cobalt is interesting as central metal cation
[1–3]. Mercaptans and other sulfur compounds, such
because of features of its electronic structure. Cobalt
as thiocarbamates, contained in gasoline and naphtha
fractions of refined oil and in liquefied propane-butane
mixtures, are extremely dangerous because of their
high toxicity, potential threat to the environment of the
environment and poisoning of the catalyst that reduces
the quality and increases the cost of refining technology
2+
7
cation (Co ) has electronic configuration [Ar] 3d
4
0
s and it is coordinatively unsaturated as a part of
the metallophthalocyanine. The cobalt forms stable
enough molecular complex and saturates its electronic
stucture by taking the ligand (or substrate) into fifth
coordination state. Meanwhile, it is possible that ligand
[4–6]. It is therefore necessary to remove such compounds
(
for example molecular oxygen) could be coordinated
from oil. There is the simplest and most common method
II
III
into sixth coordination state due to transition Co → Co
within metal complex. Biligand complex formed in this
case is labile. It is interesting from the point of view of
mechanisms of catalytic processes [11, 12] with cobalt
◊
SPP full and ◊◊ student member in good standing
Correspondence to: Artur Vashurin, email: asvashurin@mail.ru
ꢀ
*
Copyright © 2015 World Scientific Publishing Company

2
A. VASHURIN ET AL.
phthalocyanines, that involve the transfer of electrons from
the oxidant to substrate through the macrocycle. Herewith,
CoPc-support showed good activity in catalytic oxidation
of sodium diethyldithiocarbamate of oil fraction. The
main drawback of this method is high initial concentration
of macroheterocycle solution to achieve the necessary
degree of immobilization on surface of polymer matrix.
The catalyst for oil sweetening based on sulfonated
derivatives of cobalt phthalocyanine immobilized on
the surface of polymer pretreated in plasma-chemical
plant is obtained in our work. Main advantages of CoPc-
support are technological simplicity of active component
immobilization on the surface of the carrier, high degree
of phthalocyanine anchoring, ease of application of the
catalyst in oxidation process and its stability in oxidation.
The result of plasma-chemical treatment is formation of
a large number of active groups (radicals) on the surface
givingadesirabledegreeofphthalocyanineimmobilization.
Plasma-chemical method is technologically more con-
venient because it allows activating a large area of
polymer without any chemical pollution of environment.
CoPc-support was investigated in oxidation of sodium
diethyldithiocarbamate and 2-mercaptoethanol by air
oxygen. It showed a good result. Disulfide (Thiuram E)
was obtained in reaction of sodium diethyldithiocarbamate
mild oxidation with high purity. Further obtained Thiuram
E was used for organic synthesis by our colleagues.
I
II
III
multistep transitions Co ↔ Co ↔ Co are realized.
From that point of view phthalocyanine complexes with
lanthanides is also interesting. However, the peculiarity of
such compounds is formation of multideck structures, in
which there are electronic saturation and steric blocking
of the complexing metal [13].
Cobalt tetrasulfophthalocyanines are self-assembled
in water-alkaline mediums. That is why it is necessary
to replace them by less associated in water solutions
derivatives or fix at the supports [14–16]. Thus, oxidation
of lower mercaptans is easier in case of homogeneous
process, but oxidation of high-molecular mercaptans
of naphtha and gasoline fractions is easier in case of
heterogeneous one [17].
Duetotechnologicalfeaturesofremovingandregener-
ation of homogeneous phthalocyanine catalyst [18], it is
more effective to use cobalt tetrasulfophthalocyanine
and its derivatives heterogenized on the surface or in
volume of the support. For example, there are works
showing anchoring of cobalt tetrasulfophthalocyanine
at supports of coal-graphite fabric [19–21], silica [22–
2
4], zeolites [25, 26]. However, in case of electrostatic
anchoring or adsorption of catalyst in pores of substrate
there are desorption and leaching of catalyst during
the process. That is why covalent immobilization is
the most effective method to anchor phthalocyanine
molecule at polymer matrix. Besides, this method allows
protecting the catalyst from erosion and helps protect the
environment [27, 28].
RESULTS AND DISCUSSION
Preparation and characterization of catalyst
Increasing the size of peripheral substituent promotes
distancing of functional group from phthalocyanine
macrocycle (Fig. 1) conjugate and increasing its acidity.
It leads to a better anchoring of catalyst at the surface
of polymer. Increasing the number of sulfonic groups of
phthalocyanine molecule promotes increasing the area of
interaction of phthalocyanine with polymer matrix.
Covalent immobilization of phthalocyanine on the
support is confirmed by IR-spectral analysis (the example
of the spectrum is presented in the supplementary material
In our previous works [16, 24], catalysts were obtained
through covalent immobilization of sulfonated cobalt
phthalocyanines on the surface of silica matrix and their
catalytic activity was tested in the reaction of sodium
diethyldithiocarbamate oxidation. The results showed
an adequate effectiveness of the catalyst for oxidation of
mercaptans to disulfides. However, there is difficulty in
recycling of the catalyst caused by obturation of silica
pores.
The authors [29] reported about obtaining of
efficient catalyst through covalent anchoring of cobalt
tetrasulfophthalocyanine at aminomethylated polystyrene.
They used pyridine medium for immobilization of
phthalocyanine pretreated with thionyl chloride for the
formation of active groups on the surface. Anchoring of
macrocycle was due to sulfone-amide bond formation.
CoPc-support was reused in oxidation of wide range of
mercaptans and showed a good result. There are different
methodsofpolymermatrixpretreatmentforimmobilization
of phthalocyanines, for example chemical halogenation
of polymer [30] or joint synthesis of polymers with
metallophthalocyanines [31, 32]. In our opinion, chemical
methods of polymer pretreatment are technologically more
difficult and dangerous for environment.
-1
Figs S1 and S2). There are bands of IR-spectra at 700 cm
-1
and 1192–1197 cm undergoing transformation, they
are responsible for vibrations of sulfonic groups of
O
R
R
CoPcI: R = S OH
O
N
Co
N
N
N
N
SO3H
SO3H
N
N
CoPcII: R = O
N
SO3H
R
R
CoPcIII: R = O
Previously in our work [33, 34] the polymer
treated by microwave with further immobilization.
Fig. 1. Structure of metallophthalocyanines
Copyright © 2015 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2015; 19: 2–9

SULFONATED CO(II) PHTHALOCYANINES COVALENTLY ANCHORED AT ORGANIC POLYMERS AS CATALYST
3
-
1
CoPc. At the same time there is shift of 30–40 cm of
Cat
-
1
-1
2 R-SH
R-S-S-R
bands at 1630 cm , 1418 cm characterizing the state
of methyl group of PP. The lack of band at 970 cm
O2, pH 8-13 (NaOH)
-1
-
1
and appearance of new band at 2956 cm indicate
surface anchoring of CoPc. Obviously, besides cobalt
phthalocyanines immobilized covalently there is part
of them anchored by weak electrostatic interactions.
Simultaneously there is almost no peaks characteristic
of the carbonyl groups of polymer molecule. There
are characteristic bands of absorption at 630 nm
and 685 nm for CoPcI, 640 nm and 700 nm for
CoPcII and CoPcIII of UV-vis spectra of anchored
phthalocyanines in quinoline analysis (the example
of the spectrum is presented in Fig. S3). Degree of
anchoring of phthalocyanines was from 0.572 mmol/g
to 0.678 mmol/g. It is found that anchoring of CoPcI,
CoPcII и CoPcIII on the surface of PP occurs through
one fragment of peripheral substituent (Scheme 2a),
anchoring on the surface of Lavsan occurs through
two fragments of peripheral substituent (Scheme 2b).
It should be noted that possibility of anchoring of the
phthalocyanine on PP through two sulfonated fragments
and in case of CoPcIII through four sulfonated fragments
is not excluded.
The investigations of thermal destruction of obtained
materials were additionally carried out. Corresponding
thermograms are presented in Figs S4–S6. There is a
decrease of destruction temperature for nine degrees
in case of anchoring of CoPcII on polypropylene. It
is obviously reflects the beginning of the material
destruction with breaking of polymer-macrocycle bond.
In case of CoPcIII immobilization is occurred throug one
more adiitional bond (second sulfonic group as part of
the naphthalene fragment of phthalocyanine peripheral
substituent). It causes insignificant increasing of the
temperature of destruction beginning to 423°C. It is
interesting, that the second stage of melting on DSC
curve is appeared. The first stage of melting of hybrid
material 148–150°C reflects melting of pure polymer,
the second stage 159–160°C is probably connected
with melting of surface layer with the phthalocyanine
Fig. 2. Scheme of heterogeneous aerobic oxidation of mercaptan
to disulfide
anchoring on it. Summation of obtained spectral and
thermal data suggests primary immobilization of the
phthalocyanine on the surface of the polymer. The effects
reflected inserting of the macrocycle into the size of the
structure (changing of polymer’s elementary unit) of
polymer are not found.
Catalytic oxidation of RSH
Catalytic experiments were carried out using model
reactions proceed according to Fig. 2 in water-alkali
mediums in pH range 8–13. Optimal conditions for
plasma-solution activation of polymer by glow discharge,
initiated on surface of electrolyte solution, are ignition
current of 45 mA, time of treatment of 17 min, NaOH
solution with pH 10 [35].
Catalytic oxidation of substrates was carried out
in presence of phthalocyanine catalysts under aerobic
conditions. Investigated compounds were oxidized to
corresponding disulfides almost with 100% yield of final
product (Table 1). Air was bubbled with rate of 2 L/min
through solution of oxidized substrate during catalytic
oxidation of RSH. The end of the reaction was controlled
by external signs. There were change of solution
color from black-green to bluish-green in oxidation of
2-mercaptoethanol and loss of brown-yellow precipitate
in oxidation of N,N-diethylcarbamodithioate (DTC).
Kinetic curves of DTC oxidation are presented on Fig. 3
and Fig. S7.
Investigation of dependence of oxidation rate and
disulfide yields on pH shows that optimal pH values are
9–10 at lower values of pH yield and purity of disulfide are
not good enough. At pH > 10, alkali using was increased
but the yield and purity were not changed (Table 2).
Table 1. Aerobic oxidation of RSH to disulfides in water-alkali solution pH 10 in presence of catalyst
based on CoPcI and polypropylene matrix
a
-1
N
1
Mercaptan
Disulfide
Time, min
50
Yield, % TOF , h
97
94
62.4
72.2
2
65
a
TOF: Number of cycles per hour
Copyright © 2015 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2015; 19: 3–9

4
A. VASHURIN ET AL.
Fig. 3. Kinetic curves of DTC oxidation in presence of immobilized macrocycles on PP (1) CoPcI; (2) CoPcII (3) CoPcIII (4) H PcII
2
-3
(
5) H PcIII. pH 8 under 25°C, initial concentration of DTC is 3.62 × 10 M
2
Table 2. Yield of disulfide and time of DTC oxidation depending on pH of medium, at 25°C
N
pH
CoPcI-PP
CoPcII-PP
CoPcIII-PP
Time, min
Yield, %
Time, min
Yield, %
Time, min
Yield, %
1
2
3
4
5
6
7
8
8
70
68
67
65
65
63
63
62
88
92
93
93
94
94
94
94
56
52
52
50
50
50
49
49
92
93
94
94
94
94
94
94
52
49
46
45
45
45
44
44
94
94
95
95
95
95
95
95
8.5
9
9.5
10
11
12
13
N
pH
CoPcI-Lavsan
CoPcII-PP-Lavsan
CoPcIII-PP-Lavsan
Time, min
Yield, %
Time, min
Yield, %
Time, min
Yield, %
1
2
3
4
5
6
7
8
8
69
67
65
65
64
63
63
62
93
95
95
95
96
96
96
97
52
50
50
47
43
43
43
43
95
95
95
95
96
96
96
96
49
46
44
44
43
43
42
42
97
97
97
97
98
98
98
98
8.5
9
9.5
10
11
12
13
Results in Table 2 show that catalyst based on CoPcIII
probably caused by greater number of interactions of
catalyst with polymer. Similar investigations of catalytic
activity of polymer materials with anchored metal-free
complexes H PcII и H PcIII on their surface were carried
has the best catalytic activity. Probably, it may be caused
by better stability of macrocycle at surface due to
bindings between two sulfonated bridges. Slightly higher
activity of catalysts immobilized on the surface of Lavsan
2
2
out for comparison. Kinetic curves of DTC oxidation in
Copyright © 2015 World Scientific Publishing Company
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SULFONATED CO(II) PHTHALOCYANINES COVALENTLY ANCHORED AT ORGANIC POLYMERS AS CATALYST
5
the presence of such catalysts are presentred on Fig. 3.
[37]. Obtained blue-green precipitate was separated by
filtrating,washedwithethanol-methanolmixture(3:1)and
dried. Structure of complex was confirmed by methods of
-
5
Effective constants of the rate are 0.8 × 10 s/g and
-
5
1
.4 × 10 s/g for H PcII and H PcIII respectively that
2
2
1
is within the error is similar to the rate of non-catalytic
DTC oxidation [36]. It is consistent with the absence of
catalytic activity of phthalocyanine-ligands and shows
that polymer matrix does not affect the coordination unit
of the phthalocyanine macrocycle. Since otherwise the
carrier immobilized by metal-free macrocycles should
exhibit catalytic activity.
electronic absorption spectroscopy, IR-spectroscopy, H
-1
NMR and elemental analysis. IR spectra (KBr): n, cm
1720, 1632, 1502, 1452, 1489, 1409, 1379, 1134, 1049,
935, 770, 618. Elemental analysis for C H N O S Co,
3
2
16
8
12 4
%: C 39.51, H 1.87, N 11.53. Found C 37.82, H 1.79, N
1
11.18. H NMR (500 MHz): d , ppm 7.91 (Ar-H), 8.29
H
(Ar-H), 8.53 (Ar-H).
Thus, the obtained data shows the dependence
of oxidation reaction on pH of medium (optimal
values are 9–10) and size of peripheral substituent of
sulfonated phthalocyanine. Increasing the number of
sulfonated groups and distancing them from conjugated
phthalocyanine system led to better anchoring and
catalytic activity of macrocycle. Similar dependences are
observed in case of 2-mercaptoethanol oxidation.
Possibility of recycling of heterogeneous catalysts in
oxidation processes was investigated on the next step.
Oxidation reaction of DTC was used as model (Table S1).
After completion of the reaction, the catalyst was
mechanically removed from the reaction mixture, washed
in 100 mL of distilled water and reused.
All catalysts was used for at least seven cycles without
significant loss of catalytic activity and preactivation.
In all cycles the time of reaction and yield of disulfides
remain almost constant that is a good indicator for
heterogeneous catalyst. It should be noted that catalytic
activity of heterogenized phthalocyanines CoPcI, CoPcII
and CoPcIII is comparable to activity of homogeneous
catalyst CoPcI, and in case of CoPcIII-Lavsan catalyst
exceeds it. Significant advantage of such catalysts is
possibility of recycling without additional activation and
easy removal from the reaction mixture. Probably these
catalysts are more profitable from the technological and
economic point of view due to advantages described
above, despite of lower catalytic activity than the
homogeneous CoPcI. It let us to suggest that specific
activity of these catalysts is somparable with catalysts
traditionally used in Merox process [8–10].
Cobalt tetra-4-[(6′-sulfo-2-naphthyl)oxy]phthalo-
cyaninate. Cobalt tetra-4-[(6′-sulfo-2-naphthyl)oxy]-
phthalocyanine (CoPcII) (Fig. 1) was synthesized and
purified by a known method [38–40]. Mixture of tetra-
4[(6′-sulfo-2-naphthyl)oxy]phthalonitrile of potassium
(0.78 g, 2 mmol) and anhydrous cobalt chloride (0.065 g,
0.5 mmol) was heated with stirring to a temperature of
190–195°C and maintained in this state for 1 h. Formed
cobalt phthalocyanine was extracted from cooled reaction
mixture by dimethyl sulfoxide and precipitated from the
extract by absolute ethanol. Obtained precipitate was
filtered, washed with ethanol in a Soxhlet apparatus.
Final purification was chromatography on silica gel M 60
(eluent DMF/water in volume ratio 1:1).Yield was 0.39 g
(54%), blue-green powder, soluble in water, mixture of
DMF/water, DMSO, water-alkali solution. IR spectra
-1
(KBr): n, cm 1045 (n S=O), 1103 (n S=O), 1205 (n
s
as
Ar–O–Ar). Elemental analysis for C H N S O Co, %:
7
2
40
8
4
16
C 59.22, H 2.74, N 7.68. Found C 58.42, H 2.70, N 7.62.
1
H NMR (500 MHz): d , ppm 7.50 (Ar-H), 7.54 (Ar-H),
H
7.69 (Ar-H), 7.91 (Ar-H), 8.02 (Ar-H).
Cobalt tetra-4-[6′,8′-disulfo-2-naphthyl)oxy]phtha-
locianinate. Cobalt tetra-4-[6′,8′-disulfo-2-naphthyl)oxy]
phthalocianinate (CoPcIII) (Fig. 1) was synthesized and
purified by described above method [38–40]. 1.01 g
(2 mmol) of dipotassium 4-[6′,8′-disulfo-2-naphthyl)oxy]
phthalonitrile was used for synthesis. Yield was 0.53 g
(59%), blue-green powder, soluble in water, mixture of
DMF/water, DMSO, water-alkali solution. IR spectra
-
1
(KBr): n, cm 1039 (n S=O), 1103 (n S=O), 1210 (n
s
as
Ar–O–Ar). Elemental analysis for C H N S O Co,
7
2
40
8
8
28
%
: C 48.57%, H 2.25%, N 6.30%, S 14.39%. Found C
1
4
7
8.32, H 2.20, N 6.23. H NMR (500 MHz): d , ppm
.47 (Ar-H), 7.62 (Ar-H), 7.76 (Ar-H), 7.99 (Ar-H), 8.21
H
EXPERIMENTAL
(Ar-H), 8.59 (Ar-H), 8.94 (Ar-H), 9.06 (Ar-H).
Tetra-4-[(6′-sulfo-2-naphthyl)oxy]phthalocyaninate.
Polymer materials
Mixture of 0.001 mol of potassium salt of 4-[(6′-sulfo-
2
′-naphtyl)oxy]phthalonitrile and 0.30 g (0.005 mol) of
carbamid was heated with stirring to a temperature of
90–195°C and kept under constant conditions for 1 h
[38]. Pre-treatment of the phthalocyanine was carried out
by washing of it with 18% solution of hydrochloric acid
to a colorless filtrates. Next, the powder war dried. The
precipitate was further purified by the extraction with
ethanol in Soxhlet apparatus. The final purification was
carried out by chromatography with silica gel M60 using
mixture DMF:water (1:1) as eluent. The yield was 0.20 g
Commercialsamplesofpolymerswereusedinthework.
Nonwoven polypropylene (PP), specific density 400 g/m ,
thickness 4 mm. Nonwoven polyethylene terephthalate
2
1
2
(Lavsan), specific density 200 g/m , thickness 3 mm.
Synthesis
Cobalt phthalocyanine tetrasulfonic acid. Cobalt
phthalocyanine tetrasulfonic acid (CoPcI) (Fig. 1)
was synthesized by a known Weber–Busch method
Copyright © 2015 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2015; 19: 5–9

6
A. VASHURIN ET AL.
(
5
8
54%). Elemental analysis for C H N O S ·12H O, %: C
3.4, H 4.0, N 6.9, S 7.9. Found C 52.8, H 3.8, N 4.9, S
treatment was performed using gas discharge occurring
on the surface of electrolyte (glow discharge). The pH
value of treating solution was varied in range of 8–12
by adding distilled water and corresponding amount of
sodium hydroxide. The time of treatment was 5–30 min,
ignition current 50 mA. Samples treated by plasma
(size 1 × 1 cm, 5 × 5 and 10 × 10 cm) was immersed in
water solution of CoPcI–CoPcIII with concentration of
5 × 10 mol/L and held for 8 h under the temperature of
40°C. Next, the solvent was evaporated and the resulting
material dried under the temperature of 60°C. After
drying, the sample was washed with distilled water and
ethanol and dried in vacuum at 45°C for 20 h.
Degree of anchoring was monitored spectrally.
IR-spectra of all samples, electronic absorption spectra
(UV-vis) of CoPcI-CoPcIII solutions before anchoring
at the surface of polymer and UV-vis of solution after
washing of the material were registered to control the
degree of anchoring. Besides, there was chosen medium
with refractive index within the error equal to refractive
index of polymer-quinolone. It allowed to register UV-vis
spectra of immobilized phthalocyanines.
72
42
8
16
4
2
.1. UV-vis (DMF): lmax, nm 674, 704, 646 , 613 336;
infl
inf,
(H O): 606; (NaOH): 677 , 639; (H SO ): 849, 909, 748.
2 infl 2 4
-1
IR spectra (KBr): n, cm 1040 (n S=O), 1109 (n S=O),
1
is a blue-green powder soluble in DMF, concentrated
sulfuric acid, water-alkali solutions.
s
as
200 (n Ar–O–Ar), 1007 (H Pc). Obtained phthalocyanine
2
-5
Tetra-4-[6′,8′-disulfo-2-naphthyl)oxy]phthalo-
cyaninate. Mixture of 0.001 mol of potassium salt of
4
-[(6′,8′-disulfo-2′-naphtyl)oxy]phthalonitrile and 0.50 g
(0.008 mol) of carbamid was heated with stirring to
a temperature of 190–195°C and kept under constant
conditions for 1 h [38]. Pre-treatment of the phthalocya-
nine was carried out by washing of it with 18% solution
of hydrochloric acid to a colorless filtrates. Next, the
powder war dried. The precipitate was further purified
by the extraction with ethanol in Soxhlet apparatus. The
final purification was carried out by chromatography with
silica gel M60 using mixture DMF:water (1:1) as eluent.
The yield was 0.24 g (57%). Elemental analysis for
C H N O S ·16H O, %: C 42.9; H 3.6; N 5.5; S 12.7.
72
42
8
28
8
2
Found C 41.1; H 3.4; N 6.1; S 12.1. UV-vis (DMF): lmax
,
Coerced peak method was used as quantitative
measure of modification degree (the value of optical
density of characteristic absorption band T related to
nm 701, 674, 645 , 612 , 330; (H O): 638; (NaOH): 607,
inf
inf
2
-1
i
(
H SO ): 813, 790, 715. IR spectra (KBr): n, cm 1038 (n
S=O), 1109 (n S=O), 1228 (n Ar–O–Ar), 1012 (H Pc).
2
4
s
the optical density of the band of stretching vibrations
as
2
oth
of characteristic group T ). Measurments were carried
-1
out on bands 3620, 3415, 2970, 1600 и 860 cm . The
Immobilization of metallophthalocyanines
on the surface of polymer
most informative measurments were in bands 3620
-1
and 860 cm . This method together with electronic
spectra allows obtaining of reliable data about degree
of macrocycle anchoring on the surface of polymers.
Immobilization of metallophthalocyanines was carried
out onto the surface pretreated by plasma discharge. The
CoPc
O
S
O
OH
O
CH3
CH2
CH2
plasma treatment
CoPc
pH 8-12 (NaOH)
n
hydrolysis
n
n
PP
(a)
O
O
O
O
O
H2 H2
plasma treatment
pH 8-12 (NaOH)
H2 H2
CoPc
C
C
C
C
O
C
H
C O O
C C
H
hydrolysis
n
n
Lavsan
CoPc
O
S
O
O
S
O
O
O
CoPc
hydrolysis
H2 H2
C
C O O
C C
H
H
n
(b)
Fig. 4. Immobilization strategy of metallophthalocyanines onto the surface of activated polymer (a) PP, (b) Lavsan
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J. Porphyrins Phthalocyanines 2015; 19: 6–9

SULFONATED CO(II) PHTHALOCYANINES COVALENTLY ANCHORED AT ORGANIC POLYMERS AS CATALYST
7
Surface concentration of particles was calculated with
equation:
Equipment
Electronic absorption spectra (UV-vis spectra)
were registered in spectral range 200–1000 nm on a
spectrophotometer «Unico-2800» (USA) in quartz
cuvettes with a thickness of 1 mm and 10 mm.
IR-spectra were registered on FT-IR spectrophoto-
meter Avatar 360 FT-IR ESP in frequency range of
.
.
a
3
-2
N = (A/e) N 10 [cm ]
(1)
s
where A — optical density of macrocycle solution, e —
extinctioncoefficientof monomericordimericformofthe
solution (depends on association degree of macrocycle).
Values e of investigated macrocycles were taken from
works [39, 41]. This calculation assumes tempostabile
chromophore system during immobilization.
Elemental analysis for obtained hybrid materials
showed containing cobalt in amount of 2.25–3.16% on
weight. It is matched with containing of phthalocyanines
in samples.
-1
4
00–4000 cm .
Elemental analysis was performed using chromato-
graphic analyzer Flash HCNS-OEA 1112. Helium flow
rate was 140 mL/min, oxygen flow rate 250 mL/min,
reactor temperature 900°C.
1
H NMR was registered on spectrometer Bruker-500
(Germany) with frequency of 500 MHz, in CDCl , D O
3 2
and DMSO internal standard TMS.
Experiment of catalytic oxidation of mercaptans
to disulfides
The electric circuit of the plasma-chemical setup is
presented in Fig. 5. The anode in the gas phase was made
of copper wire of diameter 2 mm. The cathode in the
solution was made of copper or silver wire of diameter
The experiments to study the kinetics of reaction of
sodium diethyldithiocarbamate oxidation were carried
out in specially constructed cell with volume of 650 mL
in which the solution of N,N-diethylcarbamodithioate
2
mm, as well as a nickel tube of diameter 1.5 mm.
Thermal investigations were carried out with
Synchronous thermal analyzer (DSC/DTA/TG) with the
skimmer mass spectrometric analysis system of vapor
STA 409 CD/7/G company Netzsch Geraetebau GmbH;
InProcessInstruments(Germany).Operatingtemperature
range up to 2000°C. Resolution of thermobalance is
(
DTC) with concentration of 0.3 mol/L was loaded.
At the same time 0.01 g of catalyst was added. The
temperature was maintained 25°C within ± 0.05°C. The
air was fed via microcompressor with constant rate of
2
L/min. For these parameters of process, reaction takes
0
.1 mg. Measuring range of mass numbers of the mass
place in kinetic region [36]. After establishing a constant
temperature the solution was mixed and sample of 2 mL
was taken to determine initial concentration of DTC, then
compressor was turned on. This moment was taken as the
beginning of the reaction. Samples of 2 mL were taken
periodically during the experiment to determine current
concentration of DTC.
spectrum up to 1024 a.u.
Reagents and methods for their preparation
Solvents used in the work dimethylsulfoxide were
purified and kept in accordance to recommendations [42].
Inorganic salts applied for synthesis were previously
recrystallized by methods recommended in [43].
Deuterated solvents, and 2-mercaptoethanol were
purchased from Aldrich, and sodium N,N-diethylcarba-
modithioate (99%, ChemMed Synthesis, Russia) was
used without additional purification.
Method of determination of DTC concentration is
the following: 4 mL 0.08 mol/L solution of CuSO is
4
added to the sample of 2 mL. Herewith the dark-brown
precipitate of copper complex with DTC is formed.
Mixture is mixed. Then 0.005 mL of 50% acetic acid is
added to resulting mixture. Copper complex with DTC
is extracted into the chloroform layer. Optical density
of solution is determined spectrally at a wavelength of
CONCLUSION
4
36 nm. Current concentration of DTC is calculated with
help of calibration line. Oxidation of 2-mercaptoethanol
was carried out according to the method recommended
by [29].
In summary, heterogeneous catalysts based on
nonwoven polymer materials and sulfonated cobalt
phthalocyanines with extended periphery have significant
Fig. 5. Scheme of plasma-chemical plant for polymer treatment
Copyright © 2015 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2015; 19: 7–9

8
A. VASHURIN ET AL.
prospects as catalysts in oxidation of mercaptans to
disulfides. Technological simplicity of polymer activation
and catalytic process in presence of heterogeneous
catalyst, excellent yield of final product, parameters
of activity comparable with already using catalysts,
availability to recycling without activation and leaching
of catalyst reveal new field of heterogeneous catalytic
phthalocyanine systems. Especially noteworthy that the
final product of DTC oxidation is thiuram E with purity of
12. Tyapochkin EM and Kozliak EI. J. Mol. Cat. A:
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Fuel Process. Technol. 2012; 97: 15–23.
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98.5% that let our colleagues to use it without additional
purifying in organic synthesis.
Acknowledgements
1
7. Chatti I, Ghorbel A, Grange P and Colin JM. Catal.
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This work (synthesys of macrocycles and material
based on them) it was supported by Russian Science
Foundation (project no. 14-23-00204), and supported
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(
research of catalytic activity) by grant of the President
of Russia for state support of young scientists and PhDs
project MK-2776.2015.3).
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Actuators B: Chem. 2011; 160: 7–14.
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Figures S1–S7 and Table S1 are given in the
supplementary material. This material is available free of
charge via the Internet at http://www.worldscinet.com/
jpp/jpp.shtml.
2
2
2
9
3. Shen Ch, Wen Yue, Shen Zh, Wu J and Liu W.
J Hazardous Mat. 2011; 193: 209–215.
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