Phosphorylation of alkylated poly(ethyleneimine) in chloroform in the presence of cetyltrimethylammonium bromide and calix[4]resorcinarene

Article abstract of DOI:10.1007/s11172-007-0144-7

The phosphorylation of alkylated poly(ethyleneimine) with 4-nitrophenyl bis(chloromethyl)phosphinate in chloroform in the presence of cetyltrimethylammonium bromide (CTAB), calix[4]resorcinarene (CR), or their mixture was studied by UV spectrophotometry.

Full text of DOI:10.1007/s11172-007-0144-7

Russian Chemical Bulletin, International Edition, Vol. 56, No. 5, pp. 953—958, May, 2007
953
Phosphorylation of alkylated poly(ethyleneimine) in chloroform
in the presence of cetyltrimethylammonium bromide
and calix[4]resorcinarene
G. A. Gainanova, E. P. Zhil´tsova,ꢀ L. A. Kudryavtseva, S. S. Lukashenko,
A. P. Timosheva, and A. I. Konovalov
A. E. Arbuzov Institute of Organic and Physical Chemistry,
Kazan Research Center of the Russian Academy of Sciences,
8 ul. Akad. Arbuzova, 420088 Kazan, Russian Federation.
Fax: +7 (843 2) 73 2253. Eꢀmail: Zhiltsova@iopc.knc.ru
The phosphorylation of alkylated poly(ethyleneimine) with 4ꢀnitrophenyl bis(chloroꢀ
methyl)phosphinate in chloroform in the presence of cetyltrimethylammonium bromide
(CTAB), calix[4]resorcinarene (CR), or their mixture was studied by UV spectrophotometry.
The catalytic effect of CTAB and CR on the process of polymer phosphorylation was shown to
depend on the concentration of the surfactant and poly(ethyleneimine) in solution. The cataꢀ
lytic effect of the system is ascribed to the formation of poly(ethyleneimine)—CTAB,
poly(ethyleneimine)—CR, and poly(ethyleneimine)—CTAB—CR mixed aggregates. Their exꢀ
istence was confirmed by the methods of light scattering and UV spectroscopy.
Key words: poly(ethyleneimine), phosphorylation, phosphinic esters, surfactants, calixꢀ
resorcinarenes, catalysis, micelle formation.
One of the methods for controlling rates and mechaꢀ
nisms of chemical processes is the use of supramolecular
systems based on surfactants (Surf) in which supermoꢀ
lecular structures of various degree of organization can be
formed: direct and reverse micelles, microemulsions,
vesicles, and liquid crystals. The main principles of caꢀ
talysis in these systems are related to the formation of
nanoregions with specific characteristics, which makes it
possible to create the gradients of polarity and concentraꢀ
tions of solubilized reactants, which allows ruling their
reactivity to perform.1 The presence of additives capable
of forming complexes with surfactants and affecting selfꢀ
association processes in the systems can serve as an addiꢀ
tional tool for controlling their catalytic activity. Addiꢀ
tives that can recognize chemical compounds and aggreꢀ
gation are of special interest. Among them are polymers
and calixarenes prone to nonꢀcovalent interactions and
characterized by the high concentration of functional
groups.
Phosphorylated poly(ethyleneimines) are known to be
practically valuable compounds. They are used as extractꢀ
ing agents for uranium ions2 and efficient proton mediaꢀ
tors.3 Therefore, the search for new methods of their synꢀ
thesis is urgent. The use of supramolecular catalytic sysꢀ
tems can be one of the methods for solving this problem.
In the present work, we studied the kinetics and
mechanism of the reaction of alkylated poly(ethyleneꢀ
imine) 1 with 4ꢀnitrophenyl
bis(chloromethyl)phosphinate
(2) in chloroform in the abꢀ
sence and presence of cetylꢀ
trimethylammonium bromide
(CTAB) as a micelleꢀformꢀ
ing surfactant and alkylated
calix[4]resorcinarene (CR).
Branched poly(ethyleneimine) containing the nꢀtetraꢀ
decyl substituents with the molecular weight of the moꢀ
nomeric unit equal to 150 was used as polymer 1. The
degree of substitution in this compound, i.e., number of
substituted fragments of 1 per one unsubstituted group of
the polymer, was 0.3.
Results and Discussion
The mechanism of nucleophilic substitution in
phosphinate 2 was determined using the data obtained by
UV spectrophotometry and 31Р NMR spectroscopy. The
liberation of 4ꢀnitrophenol (3) detected in solutions of
polymer 1 containing no additives indicates the formaꢀ
tion of phosphorylated poly(ethyleneimine) 4 (Scheme 1).
The existence of the latter is confirmed by the results of
31Р NMR spectroscopy. Compound 4 is characterized by
the signal at δ 23.7, which corresponds to the products of
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 918—923, May, 2007.
1066ꢀ5285/07/5605ꢀ0953 © 2007 Springer Science+Business Media, Inc.

954
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
Gainanova et al.
phosphorylation to the N—H bonds4 (starting phosꢀ
phinate 2 in chloroform exhibits the signal at δ 39.5).
amine molecule to the nucleophilic substitution in the
phosphorus substrate.7 A certain influence on the process
can be exerted also by the selfꢀassociation of the polymer,
which was proved by dielcometric titration and light
scattering. The concentration plots of the orientational
polarization have breaks in concentration regions of
5•10–5—4•10–4 and 5•10–3—1.2•10–2 mol L–1 (Fig. 2)
indicating, according to known data,5 the formation of
aggregates 1 in chloroform. Structural transformations in
the systems continue to occur at a higher content of polyꢀ
mer 1 in solution. It was found by the light scattering
method that the change in the polymer concentration
from 0.04 to 0.055 mol L–1 increases, in the spherical
shape approximation, the effective radii of the aggreꢀ
gates (Reff) grow from 7 to 43 nm. An increase in the
poly(ethyleneimine) content to 0.1 mol L–1 is accompaꢀ
nied by a decrease in Reff to 33 nm. The formation of
associates capable of binding and concentrating the
phosphinate, i.e., acting as micellar catalysts, should reꢀ
sult in reaching a plateau by the concentration plots
of kobs.8 The retention of the square character of Eq. (1)
can be due to a large contribution of the catalytic coꢀ
assistance of the amino groups in polymer 1 to its phosꢀ
phorylation and/or to the favorable effect of the change in
the aggregate structure.
In the presence of CTAB, the phosphorylation of polyꢀ
mer 1 is accelerated by up to 7 times (Fig. 3, Table 1),
which can be a consequence of polymerꢀcolloidal catalyꢀ
sis.9 It is known10—12 that a polymer—micelle complex
can be formed in solutions containing a surfactant and
polymer. Numerous works devoted to this problem conꢀ
sider the mechanism of consecutive structural transforꢀ
mations in the systems. A complex of the polymer with
the aggregated surfactant is formed when the detergent
concentration increases and reaches the critical associaꢀ
tion concentration (CAC). Mixed structures continue
to form until the concentration polymer saturation is
Scheme 1
In the 1—CR and 1—CR—CTAB systems in chloroꢀ
form, the presence of a macrocycle with the OH groups
reactive toward the phosphinate does not change the diꢀ
rection of nucleophilic substitution: the products of the
reaction with phosphinate 2 in the indicated systems have
31Р NMR signals at δ 22.3 and 24.8, respectively. The
reaction products of the phosphinate with calixarene
would be characterized by the signal at δ 38.4.5,6
The plot of the observed rate constant (kobs/s–1) of the
reaction of poly(ethyleneimine) 1 with phosphinate 2 in
chloroform vs. polymer concentration is nonlinear (Fig. 1,
curve 1) and described by the equation
2
kobs = k1С1 + k2С1
,
(1)
where k1 = 0.08 L mol–1 s–1 and k2 = 0.76 L2 mol–2 s–1
at 25 °С.
The presence of the square term is characteristic of the
aminolysis of phosphorus acid esters in nonaqueous meꢀ
dia and can be attributed to the coꢀassistance of the second
kobs•102/s–1
kobs•102/s–1
exp
exp
Por •10–2/cm3 mol–1
Por •10–2/cm3 mol–1
10
8
4
3
2
1
0
0
1
2
3
С1•102/mol L–1
3
25
500
400
300
200
100
0
6
2
1
20
15
10
5
4
2
0
0
0.04
0.08
0.012
C1/mol L–1
–5
Fig. 1. Plots of the observed rate constant (kobs) of the reaction
of polymer 1 with phosphinate 2 in chloroform in the absence of
additives (1) and in the presence of CR (2) and CR—CTAB (3)
vs. polymer concentration (C1) (СCR = 2•10–4 mol L–1, СCTAB
0.1 mol L–1, 25 °С).
0.02
0.06
0.10
C1•102/mol L–1
=
Fig. 2. Orientational polarization (Porexp) of solutions of polyꢀ
mer 1 in chloroform at 20 °С.

Catalytic phosphorylation of poly(ethyleneimine)
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
955
kobs•103/s–1
kobs•102/s–1
(2•10–4 mol L–1)—chloroform system, the acceleration
of this reaction by calixarene achieved 6 times and can be
due to the formation of a polymer complex with the
macrocycle. Its existence in the absence and presence of
CTAB was proved by the methods of UV spectroscopy
and light scattering. According to available data,14 the
absorption bands in the UV spectra of calixarenes that
form complexes with amines undergo a bathochromic
40
4
5
4
3
2
2
3
30
20
10
shift. The absorption band of CR (5•10–5 mol L–1
)
in chloroform at 285 nm (25 °С) in the presence of
polymer 1 (5•10–3 mol L–1) shifts to higher waveꢀ
lengths (290.4 nm), i.e., by 5.4 nm. In the CR
(5•10–5 mol L–1)—1 (5•10–3 mol L–1)—CTAB (5•10–2
mol L–1) system, the shift of the absorption band of CR
(293.4 nm) relative to the absorption band in the CR
(5•10–5 mol L–1)—CTAB (5•10–2 mol L–1) solutions
(287.6 nm) is 5.8 nm. In addition, according to the reꢀ
sults of dynamic light scattering, the effective radius of
the aggregates formed in the 1 (0.05 mol L–1)—CR
(10–3 mol L–1)—chloroform system is 70 nm, i.e., the
volume of poly(ethyleneimine) associates in the presence
of calixarene increases by 1.7 times. A weaker effect of the
CR on the sizes of the polymer associates compared to
that of CTAB can be due to the fact that the micelles of
the latter threaded on the polymer matrix perform the
binding function for the polymer chains,15 thus favoring
interpolymeric association in the system. In the 1—CR
complexes this phenomenon occurs, most likely, to a less
extent.
1
1
0
0.1 0.2 0.3 0.4 0.5
CCTAB/mol L–1
Fig. 3. Plots of the observed rate constant (kobs) of the reaction
of polymer 1 with phosphinate 2 in CTAB solutions in chloroꢀ
form in the absence (1) and presence of CR (2—4) vs. CTAB
concentration (CCTAB) at 25 °С (С1 = 0.01 (1—3) and
0.05 mol L–1 (4), СCR = 2•10–4 mol L–1). Experiment is shown
by 1, 2, and 4; calculation is 3.
achieved, after which micellar surfactant aggregates unꢀ
bound to the polymer chain can exist in solution in paralꢀ
lel with the polymerꢀcolloidal complex (PCC).10 The forꢀ
mation of the PCC in the 1—CTAB—chloroform sysꢀ
tems under study is indicated by the data obtained by
light scattering. The effective radius of aggregates of 1
(0.05 mol L–1) in chloroform at 25 °С is 58 nm. The
radius of CTAB micelles is small. For instance, in soluꢀ
tions of CTAB (0.2 mol L–1) in chloroform at 30 °С the
radius is 0.8 nm.13 In the mixed 1 (0.05 mol L–1)—CTAB
(0.3 mol L–1) system, the Reff value increases to 88 nm,
which corresponds to an increase in the polymer aggreꢀ
gate volume by approximately 3.5 times.
In the polycomponent 1—CR—CTAB—chloroform
system, the phosphorylation of the polymer is accelerated
more strongly: by up to 45 times (see Fig. 3 and Table 1).
In the initial region of the kobs plot vs. CTAB concentraꢀ
tion the calculated overall effect of the surfactant and
calixarene is higher than the experimental value, whereas
the synergetic effect occurs with an increase in the CTAB
content (see Table 1 and Fig. 3).
In the 1—CR and 1—CTAB—CR systems, the presꢀ
ence of the latter favors the phosphorylation rate of the
polymer (see Figs 1 and 3). For example, in the 1—CR
Table 1. Catalytic effect of CTAB on the reaction of polymer 1 with phosphinate 2 in chloroform in the absence
and presence of CR (СCR = 2•10–4 mol L–1
)
СCTAB
/mol L–1
C1 = 0.01 mol L–1
C1 = 0.05 mol L–1
{kobs(1—CTAB—CR)•
kobs(1—CTAB)• {kobs(1—CTAB—CR)• {kobs(1—CTAB—CR)•
•[kobs(1)]–1
}
exp
•[kobs(1)]–1
•[kobs(1)]–1
}
•[kobs(1)]–1
}
exp
calc
0
1.0
1.9
2.4
2.5
2.5
2.6
2.8
3.9
6.7
5.5
5.7
6.8
12
15
17
18
22
45
4.9
9.4
12
12
12
13
14
19
33
2.1
3.3
4.1
4.7
4.9
6.0
7.8
9.2
—
0.01
0.02
0.04
0.06
0.1
0.3
0.4
0.7
Note. kobs are the observed rate constants of the reaction under study in 1—CTAB and 1—CTAB—CR systems.

956
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
Gainanova et al.
A400
Thus, the CTAB effect on the phosphorylation of alkyꢀ
lated poly(ethyleneimine) in chloroform in the absence
and presence of calixarene can be a consequence of the
transfer of substrate 2 from the solvent bulk into the mixed
polymer—surfactant and polymer—surfactant—calixarene
aggregates. In this case, the phosphinate is concentrated
in the PCC and the microenvironment of the reactants
(the substrate and reaction centers of the polymer)
changes. The latter fact is indicated by the increase in the
absorbance at 400 nm (A400) of the ion pair of polyamine
with 4ꢀnitrophenol liberating during the reaction in soluꢀ
tions of CTAB (Fig. 4) and higher A400 values of the ion
pair in the 1—CR—CTAB solutions compared to those of
the 1—CR solutions (Fig. 5). It is known16 that in nonꢀ
aqueous media the ion pairs of amines with 4ꢀnitrophenol
are equilibrated with formed by them complexes containꢀ
ing a hydrogen bond, and the increase in the medium
polarity shifts this equilibrium toward ion pairs.
Note that in the plots (see Fig. 3) after the increase in
kobs with an increase in the surfactant concentration,
which is characteristic of micelleꢀcatalyzed processes, the
rate constants of phosphorylation of polymer 1 increase
additionally in the region of high CTAB concentrations
followed by reaching a plateau. This is related, most likely,
to structural rearrangements in the system. Therefore, the
concentration curves were processed using the below preꢀ
sented equation corresponding to the pseudoꢀphase model
of micellar catalysis17 for the surfactant concentrations
not higher than 0.1—0.15 mol L–1
0.7
0.6
0.5
0.4
0.3
0.2
3
1
2
0
0.1 0.2 0.3 0.4 0.5
CCTAB/mol L–1
Fig. 4. Plots of the absorbance at 400 nm (A400) of the ion pair of
4ꢀnitrophenol (3) with polymer 1 in CTAB solutions in chloroꢀ
form in the absence (1) and presence of CR (2, 3) vs. CTAB
concentration (CCTAB) (С1 = 10–2 (1, 2) and 5•10–2 mol L–1 (3),
СCR = 2•10–4 mol L–1, С3 = 5•10–5 mol L–1, 25 °С, d = 1 cm).
A400
2
0.7
0.6
kobs = [km,SurfKS,Surf(СSurf – CAC) + k0]/
0.5
0.4
0.3
0.2
1
/[1 + KS,Surf(СSurf – CAC)],
(2)
where km,Surf is the reaction rate constant in the polymerꢀ
colloidal phase, KS,Surf is the binding constant of the subꢀ
strate with the aggregates, СSurf is the surfactant concenꢀ
tration, and k0 is the reaction rate constant in the solvent
bulk.
The parameters of the catalyzed reactions calculated
using Eq. (2) are given in Table 2. It can be seen from the
presented data that in the presence of calixarene the km,Surf
and CAC values increase and KS,Surf decreases. An inꢀ
crease in the polymer concentration in solutions of CTAB
and CR is accompanied by an increase in km,Surf and
KS,Surf and a decrease in the CAC. The catalytic effect of
the system (km,Surf•k0–1) decreases. The dependence of
the combined catalytic effect of the surfactant and
calixarene on the poly(ethyleneimine) content also afꢀ
fects the dependence of kobs of polymer 1 phosphorylaꢀ
tion on the polymer concentration in the 1—CR
(2•10–4 mol L–1)—CTAB (10–1 mol L–1) system (see Fig.
1; Table 3). The strongest acceleration of the process
(by up to 16 times) is observed at low concentrations of 1.
This can be due to a change in the shape of the concentraꢀ
tion dependence upon the addition of calixarene and
0.04
0.08
0.012
C1/mol L–1
Fig. 5. Plots of the absorbance at 400 nm (A400) of the ion pair of
4ꢀnitrophenol (3) with polymer 1 in CR solutions in chloroform
in the absence (1) and presence of CTAB (2) vs. polymer conꢀ
centration (C1) (СCR = 2•10–4 mol L–1, СCTAB = 4•10–4
mol L–1, С3 = 5•10–5 mol L–1, 25 °С, d = 1 cm).
CTAB to a solution of poly(ethyleneimine). In the abꢀ
sence of additives, the dependence of kobs on С1 has a
square character (see Eq. (1)), whereas in the presence of
CR and CTAB the favorable effect of the mixed associates
that obeys the laws of micellar catalysts becomes prevailꢀ
ing. Table 4 represents the parameters of the micelleꢀ
catalyzed process calculated by the equation for the initial
regions of the concentration plots of the mixed systems

Catalytic phosphorylation of poly(ethyleneimine)
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
957
Table 2. Parameters calculated by Eq. (2) for the reaction of polymer 1 with phosphinate 2
in CTAB solutions in chloroform in the absence and presence of CR (25 °С)
–1
С1
СCR
km,Surf•102
KS,Surf
/L mol–1
CAC•103
/mol L–1
k0•104
/s–1
km,Surf•k0
/s–1
mol L–1
0.01
0.01
0.05
—
0.0002
0.0002
0.24
1.6
3.3
180
56
80
1.9
18
2.8
8.8
48
120
2.7
3.3 (18)*
2.8 (5.6)*
* The catalytic effect on the process in the absence of CTAB and CR is given in parenꢀ
theses.
Table 3. Catalytic effect of the 1—CR (2•10–4 mol L–1)—CTAB
(0.1 mol L–1)—chloroform system on he phosphorylation of
polymer 1 at 25 °С
served rate constant of the reaction of CR (2•10–4
mol L–1) with phosphinate 2 in a CTAB solution
(0.1 mol L–1) at 25 °С is 4.7•10–7 s–1, and the resulting
effect of the polycomponent system on the phosphorylaꢀ
tion of polymer 1 in the considered range of polymer
concentrations is 2.7•104—2.3•105 times (see Table 3)
while that in the polymerꢀcolloidal phase is 5.5•105 times
(see Table 4).
С1
/mol L–1
kobs(1—CTAB—CR)• kobs(1—CTAB—CR)•
•[kobs(1)]–1
•[kobs(CTAB—CR)]–1
0.01
0.02
0.03
0.06
0.08
0.12
0.16
16
27200
40200
57400
102000
136000
183000
232000
9.7
8.0
6.6
5.8
3.9
3.5
Thus, in the polycomponent alkylated poly(ethyleneꢀ
imine)—cetyltrimethylammonium
bromide—calixꢀ
arene—chloroform system, poly(ethyleneimine) acts as a
nucleophilic agent toward the phosphinate and CTAB
and calixarene are catalyzing additives. The catalytic efꢀ
fect of the surfactant and macrocycle on the process of
polymer phosphorylation increases with an increase in
the CTAB content in the solution and a decrease in the
polymer concentration.
(with the lowest contribution of a possible catalytic effect
of free amino groups and structural changes in the system)
kobs = [km,1KS,1(С1 – CMC) + k0]/
/[1 + KS,1(С1 – CMC)],
(3)
Experimental
where km,1 and k0 are the reaction rate constants in the
micellar phase and in the solvent bulk, respectively; KS,1 is
the binding rate constant of the substrate with the polyꢀ
mer associates; CMC is the critical micelle concentration.
The presence of the surfactant in the solution deꢀ
creases KS,1 and increases the km,1 value and catalytic
effect of the system (km,1•k0–1). It should be noted that
the initial point of the concentration plots for the mixed
systems (see Fig. 1) corresponds to the reaction of the
phosphinate with the macrocycle. For instance, the obꢀ
Polymer 1 was synthesized by the reaction of branched
poly(ethyleneimine) (molecular weight 10000) with tetradecyl
bromide according to a known procedure.18 The molecular
weight of the monomeric units was determined by potentiometꢀ
ric titration.19,20 Phosphinate 2 and CR were synthesized as
described previously.21,22 Cetyltrimethylammonium bromide
(Sigma) was recrystallized from an acetone—ethanol mixture.
Prior to use chloroform was purified by a standard procedure.23
The kinetics of the reactions was studied by UV spectrophoꢀ
tometry from an increase in the absorbances of 4ꢀnitrophenol at
310—345 and 400 nm on a Specord UVꢀVis spectrophotometer
in temperatureꢀcontrolled quartz cells (25 °С). The reaction
rate constants were determined from the firstꢀorder equaꢀ
tion. The polymer concentration (mol L–1) was calculated
from the molecular weight of the monomeric unit. In kinetic
experiments, the concentrations of the reactants and surfacꢀ
tant were varied within 0.01—0.16 (1), 5•10–5—2•10ꢀ4 (2),
and 0.005—0.7 mol L–1 (CTAB). The CR concentration was
Table 4. Calculated by Eq. (3) parameters of the reaction of
polymer 1 with phosphinate 2 in chloroform in the presence of
CR (2•10–4 mol L–1) and CTAB (0.1 mol L–1) at 25 °С
System
km,1•102
/s–1
KS,1
CMC•103 k0•106 km,1
•
–1
/L mol–1 /mol L–1
/s–1
•k0
2•10–4 mol L–1
.
1—CR
1—CR—
—CTAB
4.4
26
9.2
4.1
0.045
0.052
0.3*
0.47** 553000
147000
The 31Р NMR spectra of the products of poly(ethyleneꢀ
imine) phosphorylation (without their isolation) formed in
1—2, 1—2—CR (0.01 mol L–1), and 1—2—CR (2•10–4
mol L–1)—CTAB (0.2 mol L–1) solutions in chloroform were
recorded on a Bruker MSLꢀ400 instrument (162 MHz) relative
to the external standard (H3PO4). At the beginning of the reacꢀ
* The kobs value for the reaction CR + 2 at 50 °С.
** The kobs value for the reaction CR + 2 in a CTAB solution
(0.1 mol L–1) at 25 °С.

958
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
Gainanova et al.
tion, the concentration of phosphinate 2 was 0.02 mol L–1, and
that of polymer 1 was 0.3 (without additives) and 0.1 mol L–1
(in the presence of CR and CTAB).
The sizes of the aggregates were determined on a PhotoCor
Complex photon correlation spectrometer for dynamic and static
light scattering. The laser radiation source was a He—Ne gas
laser with a power of 10 mW and a wavelength of 633 nm. The
signals were analyzed using a singleꢀplate multichannel correlator
conjugated with an IBM PCꢀcompatible computer. The light
scattering angle was 90°.
7. V. E. Bel´skii, L. S. Novikova, L. A. Kudryavtseva, and B. E.
Ivanov, Izv. Akad. Nauk SSSR, Ser. Khim., 1977, 1292 [Bull.
Acad. Sci. USSR, Div. Chem. Sci., 1977, 26 (Engl. Transl.)].
8. E. P. Zhil´tsova, D. B. Kudryavtsev, A. P. Timosheva, T. N.
Pashirova, I. Yu. Chumak, A. R. Panteleeva, and L. A.
Kudryavtseva, in Fizikokhimiya polimerov: sintez, svoistva i
primenenie [Physical Chemistry of Polymers: Synthesis, Propꢀ
erties, and Application], Izd. Tver Gos. Univ., Tver, 2004,
Issue 10, 194 (in Russian).
9. G. A. Gainanova, E. P. Zhil´tsova, L. A. Kudryavtseva, S. S.
Lukashenko, A. P. Timosheva, V. E. Kataev, and A. I.
Konovalov, Kolloid. Zh., 2006, 68, 585 [Colloid J., 2006, 68
(Engl. Transl.)].
The viscosity of solutions was determined on a VPZhꢀ2 capꢀ
illary viscosimeter (capillary diameter 0.56 mm) using a temꢀ
peratureꢀcontrolled cell.
Dielcometric titration was carried out according to a deꢀ
scribed procedure.24 The orientational polarization (Porexp) was
calculated by the equation
10. J. C. Brackman and J. B. F. N. Engberts, Chem. Soc. Rev.,
1993, 22, 85.
11. J. Kotz, S. Kosmella, and T. Beitz, Prog. Polym. Sci., 2001,
26, 1199.
12. A. F. Thunemann, Prog. Polym. Sci., 2002, 27, 1473.
13. S. V. Kharlamov, E. P. Zhil´tsova, G. A. Gainanova, L. A.
Kudryavtseva, A. P. Timosheva, A. V. Aganov, and Sh. K.
Latypov, Kolloid. Zh., 2006, 68, 550 [Colloid J., 2006, 68
(Engl. Transl.)].
14. C. D. Gutsche, M. Igbal, and I. Alam, J. Am. Chem. Soc.,
1987, 109, 4314.
15. K. N. Bakeev, S. A. Chugunov, T. A. Larina, V. Dzh.
Maknait, A. B. Zezin, and V. A. Kabanov, Vysokomol.
Soedin., Ser. A, 1994, 36, 247 [Polym. Sci., Ser. A, 1994, 36
(Engl. Transl.)].
Porexp = 3•103•С–1[(ε12 – ε )/(ε + 2)2 –
1
1
– (n122 – n12)/(n12 + 2)],
where С is the concentration of the dissolved compound
(mol L–1); ε is the dielectric constant, n is the refraction index;
indices 12 and 1 concern the solution and solvent, respectively.
The ε values of solutions were determined on a setup consisting
of an E12ꢀI instrument, which operates in the beating mode,
and a measuring cell representing a temperatureꢀcontrolled caꢀ
pacitor.25 The refraction indices were measured on an IRPhꢀ23
refractometer. The determination error Porexp did not exceed 1%.
16. Molecular Interactions, Eds H. Ratajczak and W. J. Orvilleꢀ
Thomas, J. Wiley and Sons, Chichester—New York—
Brisbane—Toronto, 1981.
17. Advances in Physical and Organic Chemistry, Ed. V. Gold,
Academic Press, London—New York, 1970, 8.
18. F. M. Menger, L. H. Gan, E. Johnson, and D. H. Durst,
J. Am. Chem. Soc., 1987, 109, 2800.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 05ꢀ03ꢀ
08086ꢀofi_a).
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Received November 21, 2006;
in revised form March 20, 2007