Polymer International Polym Int 48 :63–68 (1999)

Kinetics and reaction mechanism of template

polymerization investigated by conductimetric
measurements. Part 1. Radical polymerization
of sodium acrylate
Caterina Cris tallini,* Andrea Villani, Luigi Lazzeri, Gianluca Ciardelli
and Antonio Ses to Rubino
Department of Chemical Engineering , Univers ity of Pis a , via Diotis alvi 2 , 56126 Pis a , Italy

Abstract : The radical homopolymerization of sodium acrylate in water in the presence of potassium
peroxodisulphate as initiator was investigator through the use of conductimetry and dilatometry. The
kinetics were monitored while varying either the monomer concentration or temperature. Initial rate
and order of reaction were determined with good accuracy in a comparative way. The conductimetric
method proved superior in monitoring the reaction progress at temperatures higher than 50ÄC, allow-
ing the activation energy of the reaction to be determined.
( 1999 Society of Chemical Industry

Keywords : conductimetry ; dilatometry ; sodium acrylate ; radical polymerization

INTRODUCTION monitor this polymerization through detection of the

The kinetic study of polymerization processes
requires the monitoring of some physicochemical
properties which change as the polymerization pro-
ceeds. Measurement of the refractive index,1 dielec-
tric constant (in a few cases2), viscosity and scattered
light,3 and also density1,4h6 have been widely used.
Other detection methods are spectroscopy (Raman,
FTIR, UV or in appropriate conditions, ýuorescence
or NMR),7 chromatography (gas or liquid chroma-
tography,8 size exclusion chromatography) and ther-
moanalysis (DSC).9h11
A polymerization process is often accompanied by
volume contraction. For this reason, dilatometry is
widely used to monitor the progress of monomer
conversion, being simple and inexpensive.1,3,12,13
The application of conventional dilatometers to poly-
merization reactions is limited by two sources of
error (when the monomer itself or its solutions are
used as recording liquid): a distortion of the menis-
cus in the capillary and an unsatisfactory dissipation
of the heat of reaction because of the viscosity
increase in the reaction mixture.
Such a difficulty was indeed encountered in the
present experimental work which deals with the
homopolymerization of sodium acrylate in aqueous
solution and on its template polymerization. To
overcome this problem, an attempt was made to
electrical conductivity of the solution. The sodium
acrylate is in fact ionized in aqueous solution ; there-
fore, if the conductivity of the formed polymer is
neglected, the ionic conductivity of the solution at
any instant of time can be related to the concentra-
tion of the monomer at that time. When following
template polymerization reactions, moreover, con-
ductimetric curves can be used to gain further infor-
mation on the mechanism of the reaction (e.g.
pick-up or zip) as will be described in the following
papers of this series.14
This paper is concerned with the critical descrip-
tion of the use of the conductimetric method for the
study of the polymerization of an ionic monomer,
sodium acrylate, and is mainly focused on a compari-
son between this method and the usual dilatometric
technique.
The total conductivity of an ionic reaction solution
results from the contributions of several species,
such as the monomers, the growing chains, eventual
dead chains and the initiator molecules. In addition,
the contribution of the growing chains is not con-
stant because their mobility changes as their size
increases. In this work, it was ürst of all assumed
that the conductivity changes were only due to the
disappearing monomers. This means, in a ürst
approximation, that the eþect of the change in pH,

* Corres pondence to : Caterina Cris tallini, Department of

Chemical Engineering, Univers ity of Pis a, via Diotis alvi 2, 56126 (Received 13 February 1998 ; revis ed vers ion received 1 June
Pis a, Italy 1998 ; accepted 7 September 1998 )

( 1999 Society of Chemical Industry. Polym Int 0959–8103/99/$17.50 63

C Cristallini et al.

the decomposition of initiator, or other factors that

can bring a contribution to the variation of the con-
ductivity of the solution, are neglected. All data were
obtained from direct experimental measurements.
This approach has been employed to investigate
the possibility of using conductimetry instead of
dilatometry to follow the progress of a poly-
merization reaction, with a good agreement of the
results, in a qualitative way, and to test the quantitat-
ive reliability of the method. The conductivity
method has the advantage of allowing a digital
recording of experimental data with computer pro-
cessing that makes an experimental curve of conduc-
tivity versus time readily available, and overcomes
the difficulties encountered in recording dilatometric
contraction. According to our knowledge, this work
represents the ürst attempt to investigate the poly-
merization of ionized monomers by conductimetric
techniques.

EXPERIMENTAL
Materials
Sodium acrylate and potassium peroxodisulphate
(KPS) were purchased from Sigma Aldrich, reagent
purity grade, and used without further puriücation.
Degassed and deionized water was used as a solvent.
Apparatus
The working approach employed parallel measure-
ments of the electrical conductivity and the meniscus
position in the dilatometer, as schematized in Fig 1.
Figure 1. Schematic des cription of the working approach.
in a 36 ml cell, under uniform stirring. The electro-
lytic cell had a geometric constant k of 0.226 cm~1.
The electrolytic cell was connected to a Metrohm
712 conductometer, working at 1 kHz frequency.
Data were processed by a control program (Labview
2.5.2, National Instruments), reporting data of the
speciüc electrical conductivity at increasing reaction
times (data were measured automatically every 10 s).

Polymerization procedure RESULTS AND DISCUSSION

Polymerizations were conducted in water at diþerent
temperatures (50, 60 and 70¡C), monomer concentra-
tions (sodium acrylate, 0.4–0.7 M) and initiator con-
centrations (KPS, 5–20 mM).
Electrical conductivity and dilatometry measure-
ments were carried out simultaneously on two identi-
cal polymerization mixtures.
The reaction apparatus was contained in a water
bath kept at constant temperature (^0.1¡C).
Typical volume contraction versus time and speciüc
conductivity versus time curves at 50¡C and 10 mM
initiator are reported in Figs 2 and 3(a), respectively.
From Fig 3(a) it is evident that, at least during the
ürst 50 min,2 at increasing polymerization times,
conductivity decreases in a linear fashion as the

Polymerization procedure
Dilatometric measurements
Volume contraction was determined at diþerent
polymerization times, using a glass 12 ml dilatometer
where polymerization was carried out under uniform
stirring. The dilatometer was ülled up with the reac-
tion mixture and enough p-xylene (as recording
liquid) to occupy the total volume of the vessel. The
lowering of the meniscus was detected, at constant
time intervals, by a cathetometer.

Conductimetric measurements
The electrical conductivity of the polymerization
mixture was determined by carrying out the reaction Figure 2. Typical volume contraction vers us time curve.

64 Polym Int 48 :63–68 (1999)


Figure 3. Typical conductivity
vers us time curve : (a) in the
firs t 50 min of reaction and (b)
for the whole monitoring
period.
meniscus displacement increases ; this trend can be
explained with the reduced mobility of the ionic
species formed during the reaction. In Fig 3(b) the
curve recorded for a longer period of time of up to
1000 min is shown to demonstrate how the data are
recorded continuously by the experimental array.
To set up a comparison between the two tech-
niques used to monitor the progress of the reaction,
it is necessary to ünd a correlation between the varia-
tion of the monitored parameter (i.e. the lowering of
the dilatometer meniscus for dilatometry and the
speciüc conductivity of the solution for
conductimetry) and the disappearance of the
monomer from the reaction solution during polymer
formation. This task is particularly complex for the
conductimetric techniques, in which the single con-
tributions of each species (monomer, initiator,
growing polymer) to the overall conductivity of the
system must be taken into account. However, in
order to look for a quantitative agreement between
the two detection methods, it was assumed that con-
ductivity changes with time only because of the con-
version of monomer to polymer.
The polymerization was considered to be termin-
ated when both the contraction of the reaction
volume (as measured in the dilatometer) and the spe-
ciüc conductivity of the polymerization reached a
stationary value (which will be indicated as the ünal
value from now on). The stability of the monitored
physical properties (reaction volume, reaction
conductivity) can in fact be assumed to be an indica-
tion that no further progress of the polymerization is
occurring. At the end of polymerization, the conver-
sion of the monomer was determined by HPLC after
calibration of the method with solutions of known
sodium acrylate concentration. A conversion of 85%
was determined in both cases.
The initial reaction rate was calculated from the
dilatometric curves as follows (all polymerizations
were carried out at constant temperature, T \ 50¡C
and initiator concentration, 10 mM). Firstly, the
experimental points, obtained from the measurement
of the volume contraction, were interpolated by
means of a linear ütting of the ürst six points (10 in
the case of C 0 \ 0.7 M). This operation was per-
M i
Polym Int 48 :63–68 (1999)
Radical polymerization of sodium acrylate
formed for the dilatometric curves concerning four
diþerent monomer concentrations : C 0 \ 0.4 M,
M
0.5 M, 0.6 M and 0.7 M, respectively. Secondly, the
slope of the linear ütting was calculated in order to
obtain an estimate of the initial reaction rate vdil
i
expressed in cm min~1. As expected, the initial poly-
merization rate increases with increasing initial
monomer concentration. Thirdly, vdil was converted
i
into vc expressed in the usual concentration unit
i
(mol l~1 min~1) by considering the ünal value of the
volume contraction (*h ) corresponding to the disap-
f
pearing of 85% (HPLC) of the initial monomer
amount (eqn 1):
lc \ 0.85 vdil C 0 /*h (1)
i i M f
Equation (1) is obtained by considering that the reac-
tion rate \ d[M]/dt \ d[M]/(V dt) \ dC/dt. This
approximated result is obtained by neglecting the
volume change during the reaction, as justiüed by
the following calculation. The total volume of the
dilatometer is 12 cm3. The meniscus displacement
occurs within a capillary tube with an inner diameter
of 1 mm. The biggest meniscus displacement (*h )
f
observed in our experiments was 4.67 cm, for a poly-
merization reaching 85% conversion. That is, the
displacement for a 100% conversion would have
been 4.67/0.85 \ 5.49 cm. This value corresponds to
a volume change of 4.32 ] 10~2 cm3 ; this is less than
0.4% of the total volume of the solution. This very
small value lead us to neglect the changes in concen-
tration due to volume changes.
Similar calculations were performed on the data
obtained by conductimetry, with the advantage that
the conductivity versus time curve is determined
directly by the instrument, and can also be ütted as
exponential decay, the number of experimental data
being much larger than for dilatometry.
In this case, the derivative of the exponential
decay for t \ 0, vcon (expressed as S cm~1 min~1) can
i
be calculated and considered as an estimate of the
initial velocity. Alternatively, this value can be deter-
mined from the slope of a linear ütting of the experi-
mental points at the beginning of the polymerization.
Values of vc obtained with the two methods were
65
C Cristallini et al.

indeed very close. Assuming in this case that the

total conductivity decrease (*s ) is only due to the
f
disappearance of the monomer, we can propose eqn
(2) for conductimetry :

vc{ \ 0.85 vcon C 0 /*s (2)

i i M f
which is similar to eqn (1), and valid under the same
approximation of neglecting the volume change
during reaction. Changes of conductivity due to
volume changes were neglected for the same reasons
as for dilatometry. Values thus calculated are report-
ed in Table 1.
Figure 4. Convers ion vers us time plot obtained by means of
On the basis of the above deünition, the conver- dilatometry (=) and conductimetry (line at half height) with C 0 \
sion will be correlated with the lowering of the M
0.4 M, T \ 50¡C and initiator concentration of 10 mM.
meniscus (dilatometry) or the conductivity of the
solution (conductimetry) by means of eqn (3): comparable data are obtained for the initial reaction
rate with the two methods. Comparison of the values
Conversion (x or x ) \ 0.85 of the last two columns on the left, indicate that
d c
] [val(t) [ val(t \ 0)]/val(end) (3) slightly lower values are obtained by conductimetry ;
however, the ratio between the two values is quite
constant (i.e. vc{ is about 0.8vc), suggesting a good
where val(t) is the meniscus displacement or solution i i
stability of the methods with changing initial
conductivity at instant t, val(t \ 0) is the meniscus
monomer concentrations. The accord between the
displacement or solution conductivity at the begin-
two methods, with respect to the relative change of
ning of the polymerization, val(end) is the meniscus
reaction rate upon changing the initial monomer con-
displacement or solution conductivity at the end of
centration, becomes more evident from the analysis
the polymerization (see above) and 0.85 is the con-
of Fig 5 where the ratio between initial reaction rates
version determined by means of HPLC at the end of
at varying C 0 values and that at C 0 \ 0.4 M is
the polymerization (see above). (The variation of the M M
reported on a logarithmic scale (ln(v/v(C 0 \ 0.4)) as
monitored physical properties is proportional to the M
a function of ln(C0 /(C 0 \ 0.4)). The data obtained
amount of monomer polymerized.) For example, in M M
the case C 0 \ 0.4 we shall use for dilatometry value
M
(t \ 0) \ 0, ünal value \ *h \ 2.68 cm ; and for
f
conductimetric measurements value (t \ 0)\ 0.03626;
ünal value \ *s \ 0.01082 S cm~1. Then we shall
f
calculate the conversion by means of eqn (3).
The two sets of conversion data are compared in
Fig 4, where conversion values are calculated for
each experimental point taken during the ürst 100
min of reaction. The conversion versus time curves
were obtained by the two methods with good agree-
ment. The scattered data obtained by dilatometry
can be ascribed to the manual and discontinuous
procedure used for measuring the lowering of the
meniscus in the capillary tube. The scattering is of
course absent in the conductimetric curve which is
Figure 5. Logarithmic plot of the ratio (v /v (C 0 \ 0.4)) between
gained by a continuous computerized automatic M
reaction rates at varying C 0 values and that for C 0 \ 0.4 M, as a
array. M M
function of (C 0 /0.4) : dilatometry (L) and conductimetry ( ] ). The
Results reported in Table 1 show clearly that, even M
s lope of the linear fitting (s olid line) gives the order of reaction
with the approximation assumed in calculations, with res pect to the monomer.

C0 v dil ] 103 v con ] 103 v c ] 103 v c{ ] 103

M i i i i
(mol l É1) (cm min É1) (S cm É1 min É1) (mol l É1 min É1) (mol l É1 min É1)
Table 1. Values obtained for
the initial reaction rate from 0.4 8.84 0.02967 1.121 0.9323
dilatometry (v c) and 0.5 11.79 0.04624 1.764 1.416
i
conductimetry (v c{) 0.6 17.92 0.05644 2.355 1.928
i
and parameters us ed in 0.7 26.45 0.07756 3.370 2.798
their calculation

66 Polym Int 48 :63–68 (1999)

 Radical polymerization of sodium acrylate

from the two methods exhibit a scattering which is
barely detectable.
The diþerence in the initial reaction rate obtained
with dilatometry and conductimetry could be due to
some physicochemical reason that makes some
approximation not completely correct, therefore
aþecting the calculated value, or to some systematic
error of one or both measuring methods. On the
basis of the above experimental data it is possible to
evaluate the external reaction order with respect to
monomer concentration. Equation (4) shows the
polymerization rate of sodium acrylate in the pres-
ence of potassium peroxodisulphate as initiator (C ):
I
v \ kC a C b
M I
which at constant initiator concentration becomes
v \ kC a C b \ k@C a
M I M
Therefore, expressing eqn (5) in a logarithmic form
ln v \ ln k@ ] a ln C
M 50
the order of reaction with respect to monomer can be
derived from the slope of the linear graph ln v
r v
versus ln C 0 , which is reported in Fig 6 for both
M
dilatometry and conductimetry measurements. The
calculated values are reported in Table 2.
As shown in Fig. 6, two parallel straight lines are
obtained from the interpolation of data obtained by
the two methods. The slope of these curves gives the
order of reaction with respect to the monomer for the
polymerization of sodium acrylate. A value of 1.9
was obtained in both cases, showing that the deter-
mination of this parameter can be obtained by dila-
tometry and conductimetry with very good precision.
This value corresponds to the slope of the linear
ütting for data shown in Fig. 5. Data available in the
literature show that, although an order of reaction of
unity should be expected, a value higher than unity
can be experienced in some conditions as reported
for acrylic acid,15h16 methyl methacrylate,17 and
acrylamide.18
In order to determine the activation energy, mea-
surements were conducted at constant monomer
(0.5 M) and initiator (10 mM) concentration while
varying the temperatures (T \ 50, 60, 70¡C). From
(4) the well-known Arrhenius equation we know that
k \ A exp([E /RT) (7)
a
(5) which gives the dependence of a kinetic constant
upon the absolute temperature (T), where A and R
are constants and E is the activation energy of the
a
reaction. If we suppose that v is the reaction rate at
0
(6) 50¡C (v ) we obtain
ln
v E 1
\[ a [
1A B (8)
R T 323
50
and the activation energy is obtained as the slope of
the curve ln v/v versus 1/T multiplied by [R.
50
Experimental points and the corresponding linear
ütting are reported in Fig 7. Values measured and
calculated are summarized in Table 3. All data were
obtained from conductimetric measurements,
because the experimental arrangement for the dila-
tometric method proved not to be well-suited to

Figure 6. Plots of the logarithms of initial reaction rate vers us

ln C 0 obtained from dilatometric (=, s olid line) and Figure 7. Plot of ln v /v vers us 1/T with values obtained from
M 0
conductimetric (…, dotted line) meas urements . conductimetric meas urements .

C0 v c ] 103 v c{ ] 103 ln C 0 ln v c ln v c{
M i i M i i
(mol l É1) (mol l É1 min É1) (mol l É1 min É1)
Table 2. Values obtained for
the order of reaction with 0.4 1.121 0.9323 [0.9163 [6.717 [6.978
res pect to monomer 0.5 1.764 1.416 [0.6931 [6.34 [6.56
concentration from dilatometry 0.6 2.355 1.928 [0.5108 [6.051 [6.251
(v c) and conductimetry (v c{), 0.7 3.370 2.798 [0.3567 [5.599 [5.879
i i
and parameters us ed in their Order of reaction 1.937 1.929
calculation

Polym Int 48 :63–68 (1999) 67

C Cristallini et al.
Table 3. Values determined for the calculation of the
activation energy of the radical polymerization of
s odium acrylate (an E value of 14.3 kcal molÉ1 was
a be compared to those obtained by the usual dila-
obtained)
T (¡C ) 1/T v c{ ] 103 \ v ln v /v
i 50
(K É1) (mol l É1 min É1)
50 0.0031 1.416 0
60 0.003 2.597 0.6065
70 0.0029 5.987 1.44
follow the reaction at temperatures higher than 50¡C
owing to the enhanced polymerization rate. From the
extrapolation of these data an E value of 14.3
a 1 Stickler M, Makromol Chem Macromol Symp 10/11 :17 (1987).
kcal mol~1 is obtained in this temperature range.
CONCLUSIONS
Results shown in this paper clearly indicate the
possibility of using conductimetry to follow the poly-
merization reaction of an ionic monomer such as
sodium acrylate in water. A decrease of conductivity
is observed during polymerization as a consequence
of the lower mobility of the ionic species of the
polymer chains, giving qualitative information about
the progress of the polymerization. Some, kinetic
parameters, such as initial reaction rate and external
order of reaction with respect to monomer concen-
tration, can be derived from the conductimetric
curve, in fairly good quantitative accord with the
same parameters derived from the more usual dila-
tometric technique. In our work, moreover, we expe-
rienced several difficulties in determining the
activation energy of the reaction by taking dila-
tometric measurements at temperatures higher than
50¡C. In contrast, these difficulties were not encoun-
tered when following polymerization by the conduc-
timetric technique, thus allowing a reasonable value
for the activation energy to be determined. Future
work will be devoted to showing how the conducti-
metric method can be applied to monitoring the
68
polymerization of other ionic monomers in the pres-
ence of preformed macromolecules. The results will
tometric technique. The conductimetric method will
be also used as a diagnostic tool to obtain more
reliable information on the mechanism of template
polymerization, with respect to dilatometry.
ACKNOWLEDGEMENTS
The authors thank Dr Giovanni Polacco for his
support and for fruitful discussions.
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Polym Int 48 :63–68 (1999)