Kinetics of Chemical Oxidative Dispersion

Polymerization of 3,5-Xylidine in Aqueous Medium Using

a pH Stat Method
H. MINAMI, M. OKUBO, K. MURAKAMI, S. HIRANO
Department of Chemical Science and Engineering, Faculty of Engineering, Kobe University, Kobe 657-8501, Japan

Received 18 May 2000; accepted 6 September 2000

Kinetics of chemical oxidative dispersion polymerization of 3,5-xylidine

(Xy) in aqueous medium with ammonium persulfate (APS) as an oxidant was studied
by monitoring the amount of proton released from Xy monomer, which was obtained
from the amount of potassium hydroxide (KOH) solution added to keep constant pH
values using a pH stat. The initial polymerization rate (R) [mol/L/min] of Xy was
expressed as follows: R 1.65 (1 ) [Xy] [APS], where is the degree of ionization of
Xy, and [Xy] and [APS] are concentrations of Xy and APS, respectively. 2000 John Wiley

ABSTRACT:

& Sons, Inc. J Polym Sci A: Polym Chem 38: 4238 4246, 2000

Keywords: 3,5-xylidine; chemical oxidative dispersion polymerization; kinetics; ionization

INTRODUCTION
Chemical oxidative polymerization of nonvinyl
monomers such as pyrrole, aniline, and their derivatives has been studied in recent years.19
Armes and coworkers reported that polypyrrole
particles were produced by chemical oxidative polymerization in aqueous solution using iron (III)
chloride. Pressed pellets of the freeze-dried particles had solid-state electrical conductivities as
high as 15 S/cm.1 Abe and coworkers showed
that the chemical oxidative polymerization of aniline in HCl aqueous solution was possible with
ammonium persulfate (APS) as an oxidant.2
Spherical and needle-shaped polyaniline particles
were produced using various stabilizers by Vincent and Waterson.3 Snauwaert et al. carried out
polymerizations of dimethylanilines using APS or
This study is Part CCV of the series Studies on Suspension and Emulsion.
Correspondence to: M. Okubo (E-mail: okubo@cx.kobe-u.
ac.jp)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 38, 4238 4246 (2000)
2000 John Wiley & Sons, Inc.

4238

potassium dichromate as an oxidant, and pointed

out that 3,5-xylidine (Xy) did not give polymeric
products.10 Toshima and Yan also reported that
no polymeric products was obtained from Xy with
APS.11 However, we tried chemical oxidative polymerization of Xy, which has appropriately low
solubility in water from the point of view of particle production, and found the synthesis of spherical and needle-shaped particles by chemical oxidative dispersion polymerization of Xy with APS
in aqueous medium.12
Although many papers on the preparations and
properties of aniline and its derivatives have been
published, the kinetics and mechanism have been
not clearly understood. Some groups have recently studied the kinetics of aniline and its derivatives by electrochemical and chemical oxidative polymerizations in aqueous medium using
gas chromatography,13,14 linear sweep cyclic voltammetry,15 calorimetry,16 electron absorption
spectroscopy,14,17 and proton NMR spectroscopy.18 In those experiments, the reaction mechanism may have changed during polymerization
because the solution pH decreases with increas-

DISPERSION POLYMERIZATION OF XYLIDINE

4239

at 250 rpm with a magnetic stirrer at various

constant pH values using a pH stat (TOA Electronics Limited; ABT-511). The pH value was
measured with a glass electrode, and 0.5 N KOH
solution was added continuously from the pH stat
to keep a constant pH value in the system. The
amount of released proton during the polymerization was calculated from the amount of KOH
added with the pH stat to keep the pH value
constant.
pKa Measurements
The pKa value of Xy measured by potentiometric
titration with 0.01 N HCl was 5.06. The degree of
ionization of Xy at each pH was calculated with
this value.
Figure 1. Typical timepH curve at 25 C in the
chemical oxidative dispersion polymerization of 3,5xylidine listed in Table I.

ing conversion. This pH drift affects the ionization of the monomer (aniline or Xy). Surprisingly,
to the best of our knowledge there is no paper
dealing with the polymerization kinetics of aniline and its derivatives from the viewpoint of the
ionization of monomer.
In this article, the kinetics of polymerization of
Xy with APS in aqueous medium is discussed
from the amount of released proton from Xy
monomer during polymerization at various constant pH values using the pH stat method.

EXPERIMENTAL
Materials
We used Xy, APS, hydrochloric acid, and potassium hydroxide (KOH) of analytical grade as received from Nacalai Tesque Co. Deionized water
with a specific conductivity of 5 106 cm was
distilled once with a Pyrex distillator. Poly(vinyl
alcohol) (PVA) was supplied by Nippon Synthetic
Chemical (Gohsenol GH-17: degree of polymerization, 1700; degree of saponification, 88%).
Chemical Oxidative Dispersion Polymerization
The chemical oxidative dispersion polymerization
of Xy in aqueous medium was carried out in a
glass cylindrical reactor at various temperatures

Gas Chromatography
The amount of unpolymerized Xy monomer was
determined by gas chromatography (Shimadzu
GC-18APFsc). A capillary column (HR-20M, 30 m
0.32 mm i.d., 1.0 m film thickness; Shinwa
Chemical Industries, Ltd.) was used with helium
as a carrier gas.

RESULTS AND DISCUSSION

Figure 1 shows the time dependence of pH in the
chemical oxidative dispersion polymerization of
Xy in aqueous medium at 25 C under the conditions listed in Table I. The pH value in the system
monotonously decreased with the polymerization
time, which was due to release of proton from the
Xy monomer.
Figures 2 and 3 show variations of the amounts
of 0.5 N KOH solution consumed to keep pH 7

Table I. Recipes for Production of Poly(3,5-xylidine)

Particles by Chemical Oxidative Dispersion
Polymerization in Aqueous Mediuma
Ingredient

(g)

(mmol)

3,5-Xylidine
APS
PVA
Water

0.40
1.51
0.12
100

3.3
6.6

a
Stirring rate, 250 rpm, various constant temperatures
(C): 0, 10, 20, 25, 30, 40, adjusted at constant pH values of 3,
4, 5, 6, and 7 with 0.5 N KOH using pH stat. APS ammonium persulfate; PVA poly(vinyl alcohol).

4240

MINAMI ET AL.

In this reaction, 2 mol of Xy monomer reacted

with 1 mol of APS, resulting in 1 mol of the dimer
and 2 mol of proton as below:

Because the number of released proton is the

same as the number of Xy monomer consumed in
the polymerization, at any given time [Xy] and
[APS] can be expressed as follows.
Xy Xy 0 H
APS APS 0
Figure 2. Variations in amounts of 0.5 N KOH consumed to keep constant pH as a function of time in
chemical oxidative dispersion polymerizations of 3,5xylidine at 25 C at various 3,5-xylidine concentrations
(wt % based on water) listed in Table II: E, 0.05; K, 0.1;
M, 0.2; N, 0.3; F, 0.4.

constant in the chemical oxidative dispersion polymerizations of Xy at various Xy and APS concentrations listed in Tables II and III, respectively. These results indicate that the amounts of
released proton increased with the increases in
the Xy and APS concentrations, respectively.
Each initial release rate of proton was decided
from the initial slope of each curve.
Figures 4 and 5 show the relationships between the Xy and APS concentrations and the
initial release rate of proton at pH 7, respectively.
These plots were linear; therefore, the initial release rates of proton were first order in the concentrations of Xy and APS, respectively. Accordingly, the release rate of proton at the initial step
of the polymerization is expressed as follows:
dH
kXyAPS
dt

dH
Ln k LnXy LnAPS
dt

H
2

(4)

where [Xy]0 and [APS]0 are the initial Xy and APS

concentrations (mol/L), respectively. By substituting eqs 3 and 4 into eq 1, eq 5 is given as

dH
H
1.65Xy 0 H APS 0
dt
2

(5)

under a boundary condition that [H] is zero at t

0. The amount of released proton is expressed
as in eq 6.

(1)

where [H] is concentration (mol/L) of released

proton, [Xy] and [APS] are concentrations (mol/L)
of Xy and APS, respectively, and k is a rate constant (L/mol/min). The k value calculated from
the intercept in Figures 4 and 5 using eq 2 was
1.65 L/mol/min at 25 C.
Ln

(3)

(2)

Figure 3. Variations in the amounts of 0.5 N KOH

consumed to keep constant pH 7 as a function of time in
chemical oxidative dispersion polymerizations of 3,5xylidine at 25 C at various APS concentrations (molar
ratio to 3,5-xylidine) listed in Table III: E, 0.1; K, 0.5; M,
1.0; N, 2.0; F, 3.0.

DISPERSION POLYMERIZATION OF XYLIDINE

4241

Table II. Recipes for Production of Poly(3,5-xylidine) Particles by Chemical

Oxidative Dispersion Polymerizationa at pH 7b
3,5-Xylidine (wt %)c
Ingredient (g)
3,5-Xylidine
APS
PVA
Water

0.05

0.1

0.2

0.3

0.4

0.05
1.51
0.12
100

0.10
1.51
0.12
100

0.20
1.51
0.12
100

0.30
1.51
0.12
100

0.40
1.51
0.12
100

25 C; stirring rate, 250 rpm.

Adjusted with 0.5 N KOH using pH stat.
Based on water.
APS ammonium persulfate; PVA poly(vinyl alcohol).

b
c

H Xy 0
2APS 0 Xy 0

Xy 0
2APS 0

Xy 0
exp0.8252APS 0 Xy 0t
2APS 0

(6)

Figure 6 shows the time dependence of the released proton concentrations calculated from eq 6
(line) and its experimental values (circles) as a
function of polymerization time at pH 7. At the
initial step of the polymerization, a good correspondence was observed. However, as the polymerization proceeded, they did not agree well.
The disagreement may be based on the proton
released from the oxidation of oligomer. In fact,
the system became turbid after several minutes
because of precipitating oligomers.
Figure 7 shows the amounts of 0.5 N KOH
solution consumed to keep constant at various pH
values at 25 C in the chemical oxidative dispersion polymerization of Xy listed in Table I. The

pH value in the system clearly affected the

amount of released proton. The release rate and
amount of proton increased with an increase in
the pH value.
Figure 8 shows the relationship between the
unionization Xy concentration and the initial release rate of proton at various pH values. This
plot was linear, and the initial release rate of
proton was first order in the unionization Xy concentration, which depends on the pH value in the
system. In some papers, polymerization of aniline
in acidic medium had an induction period16,19 and
the k value was three orders of magnitude smaller13 than that in this work. The reason seems to
be based on neglecting the ionization of aniline. In
acidic medium, the concentration of unionization
monomer is extremely low. The release rate of
proton at the initial step of the polymerization is
rewritten as follows.
dH
1.651 XyAPS
dt

Table III. Recipes for Production of Poly(3,5-xylidine) Particles by Chemical

Oxidative Dispersion Polymerizationa at pH 7b
APS/3,5-Xylidine (Molar Ratio)
Ingredient (g)
3,5-Xylidine
APS
PVA
Water
a

0.1

0.5

1.0

2.0

3.0

0.40
0.075
0.12
100

0.40
0.38
0.12
100

0.40
0.75
0.12
100

0.40
1.51
0.12
100

0.40
2.26
0.12
100

25 C; stirring rate, 250 rpm.

Adjusted with 0.5 N KOH using pH stat.
APS ammonium persulfate; PVA poly(vinyl alcohol).

(7)

4242

MINAMI ET AL.

Figure 4. Relationship of 3,5-xylidine concentration

and initial release rate of proton at pH 7.

where degree of ionization of Xy. Equation 8

is given from eq 7 with a boundary condition that
[H] is zero at t 0.
H Xy 0
2APS 0 Xy 0

Xy 0
2APS 0

exp0.8251 2APS 0 Xy 0t

Xy 0
2APS 0

Figure 6. Time dependence of the released [H] values () calculated by eq 1 with rate constant (k) of 1.65
(L/mol/min) and experimental values (E) using pH stat
at pH 7.

Figure 9 shows the variations of the released proton concentrations calculated from eq 8 (line) and
its experimental values (open circles) and conversion (closed circles) of Xy measured by gas chromatography as a function of the polymerization
time at various pH values. In most pH systems,

(8)

Figure 5. Relationship of APS concentration and initial release rate of proton at pH 7.

Figure 7. Variations in the amount of 0.5 N KOH

consumed to keep constant pH as a function of time in
chemical oxidative dispersion polymerizations of 3,5xylidine at 25 C listed in Table I. pH values: E, 3; K, 4;
M, 5; N, 6; F, 7.

DISPERSION POLYMERIZATION OF XYLIDINE

4243

lease rate of proton expresses the initial polymerization rate of Xy.

On the other hand, in the systems of pH 4 and
5, the calculated proton concentration values did
not agree with those measured experimentally,
although the systems were not turbid within the
observed time. The disagreement was caused by
two kinds of release protons at the initial step,
which are shown as follows.

Figure 8. Relationship of unionized 3,5-xylidine concentration and initial release rate of proton.

the conversion gave good agreement with the concentration of released proton calculated from eq 8.
These results suggest that eq 8 led from the re-

H (A) is released from Xy molecules during

the polymerization, and H (B) is released owing to ionization equilibrium by the consumption of Xy during the polymerization step. In the

Figure 9. Time dependence of the released [H] values () calculated by eq 5 with

rate constant (k) of 1.65 (L/mol/min), experimental values (E) using pH stat and
conversion (F) of 3,5-xylidine by gas chromatography at various pH values.

4244

MINAMI ET AL.

Figure 10. Time dependence of the released [H] values () calculated by eq 7 with
rate constant (k) of 1.65 (L/mol/min) and experimental values (E) using pH stat at
various pH values.

systems of pH 6 and 7, almost all Xy is unionized. On the other hand, in the system of low pH
value most of Xy is ionized. Thus, in the poly-

merization, the two kinds of released protons

must be considered. The former ([H]A) is expressed the same as eq 8.

Figure 11. Variations in the amounts of 0.5 N KOH

consumed to keep constant pH 7 as a function of time in
chemical oxidative dispersion polymerizations of 3,5xylidine at various temperatures: E, 0 C; K, 10 C; M,
20 C; L, 30 C; F, 40 C.

Figure 12. Arrhenius plot of the logarithm of rate

constant (k) versus the reciprocal numbers of temperature (1/T).

DISPERSION POLYMERIZATION OF XYLIDINE

4245

Figure 13. Possible scheme for chemical oxidative polymerization of 3,5-xylidine.

H A Xy 0
2APS 0 Xy 0

persion polymerization of Xy. According to the

Arrhenius law,

Xy 0
2APS 0

Xy 0
exp0.8251 2APS 0 Xy 0t
2APS 0
(9)

The latter ([H]B) is as follows:

H B H A

(10)

Adding eqs 9 and 10, the amount of released

proton with time is expressed as follows.
H 1 Xy 0
1 2APS 0 Xy 0

Xy 0
2APS 0

exp0.8251 2APS 0 Xy 0t

Xy 0
2APS 0
(11)

Figure 10 shows the time dependences of the released proton values calculated from eq 11 (line)
and those measured experimentally (open circles)
as a function of polymerization time at various pH
values. At each pH system, the agreement between experimental and calculated data became
better than that in Figure 9.
Figure 11 shows the amounts of 0.5 N KOH
solution consumed to keep constant pH 7 at different temperatures in the chemical oxidative dis-

Ln k Ln A Ea/RT

(12)

where Ea is the activation energy, R is the gas

constant, and T is the reaction temperature (K),
respectively. The Arrhenius plot of the logarithm
of k versus the reciprocal number of temperature
(1/T) for the polymerization of Xy is shown in
Figure 12, in which k was calculated from the
initial slope of each curve. This plot was linear,
indicating that the reaction obeyed the Arrhenius
law. The activation energy calculated from the
slope was 43 kJ/mol. This value is comparable to
that of oxidation of monomer for electrical oxidative polymerization of aniline.20
From the above results, we conclude that the
chemical oxidation dispersion polymerization of
Xy starts from unionized Xy with APS as shown
in Figure 13, and the initial polymerization rate
at 25 C was expressed as k(1)[Xy][APS] (k:
1.65 L/mol/min).

REFERENCES AND NOTES

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4246

MINAMI ET AL.

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