Sulfonation Reaction Kinetics of Polystyrene

(Ethylene Butylene) Polystyrene

Elamathi S *, Usha D** and Sangeetha D***

Sulfonation kinetics of polystyrene-block-poly-( ethylene-ran-butylene)-block-

polystyrene (PSEBS) has been studied using chlorosulfonic acid as the sulfonating
agent in chloroform medium. Sulfonation was observed at 32 DCand 58 DCusing
UV-visible spectroscopy. Fractional sulfonation has been calculated from the spectral
absorption of the reaction system. The reaction was found to be of the first order with
respect to the concentration of the polymer. The reaction follows the Arrhenius equation
over the temperature range of the study (0-58DC)and the activation energy was calculated
to be 3.3 kJ/mo!.

Keywords: Pol ystyrene- block -pol y-(eth ylene-ran -bu tylene)- block -pol ystyrene, Kinetics,
Sulfonation

Introduction
Polystyrene(ethylene butylene) polystyrene(PSEBS)(Weissand Sen, 1991)is an aromatic
polymer with sulfonation at the phenyl ring. Sulfonated phenyl ring is of great interest as
the solution-cast membranes offer proton conductivities that compete with those of
perfluorosulfonate ionorner membranes such as Nafion (Curtin et al., 2004). Promising
data have been reported for its suitability in hydrogen-oxygen (Curtin et al.) and direct
methanol fuel cells (Park and Yamazaki, 2005) in earlier reports. The kinetics of aryl
sulfonation is being studied since 1908. Most of the studies showed that the rate is
proportional to the aromatic ring concentration. Akovali and Ozkan (1986) reported the
sulfonation kinetics of polystyrene in sulfuric acid and found that only the para position
of the phenyl ring was sulfonated and also that the rate was of the first order with respect
to the polystyrene repeat unit. Shibuya and Porter, 1992 studied the kinetics of Poly
(Ether Ether Ketone) (PEEK) sulfonation using sulfuric acid (Reynolds et al., 1991).
Sulfonation reaction kinetics of Poly (Ether Ketone Ketone) (PEKK) using a mixture of
concentrated and fuming sulfuric acid was studied by Swier et al., 2004. However, no
* Research Scholar, Department of Chemistry, Anna University, Chennai 600025, India.
E-mail: elamathe@gmail.com
** Student, Department of Chemistry, Anna University, Chennai 600025, India.
E-mail: usha24091984@yahoo.co.in
*** Lecturer, Department of Chemistry, Anna University, Chennai 600025,India; and the corresponding
author. E-mail: sangeetha@annauniv.edu

@ 2009 The Icfai University Press. All Rights Reserved.

 systematic study has been conducted on the kinetics of sulfonation of PSEBS. In this
work, we have studied the reaction kinetics ofPSEBS sulfonation by chlorosulfonic acid
in chloroform at highly dilute conditions. With chlorosulfonic acid as the sulfonating
agent, the reaction rat~ was found to be of the first order with respect to both the polymer
as well as the sulfonating agent.

In this study, sulfonation analysesbased on ultraviolet (UV)-visible spectroscopy were

carried out. This method is an efficient one for quantitatively analyzing compounds
possessing double bonds (such as an aromatic structure). The spectroscopy has been
widely applied to kinetic studies (Shibuya and Porter, 1994) since the simple and fast
measurement can give accurate and direct analyses of reaction mixtures. Generally, the
UV-visible spectra of aryl compounds are measured in highly dilute conditions, due to
large absorption coefficient of the compounds.

For the measurement of reaction progress, the fractional sulfonation (X) per chain
repeat unit is calculated from the following ratio:

x = (/- 10)/(la - 10) ...(1)

where /, /0 and / arepresent the absorbance at a time t, at the reaction starting point (t = 0)
and at the reaction ending point (t = a).

Materials and Methods

Polystyrene- block-poly-( ethylene-ran -bu tylene)- block-polystyrene (PSEB S)
(Mv = 89,000; 29%styrene) was obtained from Aldrich, Germany. Chlorosulfonic Acid
(CSA)was purchased from Spectro-chem, India, and used without further purification.
Tri-Butyl Phosphate (TBP) (Lancaster) and Methanol (SRL) were purchased and used
as received. The solvent used for membrane casting was Tetrahydro Furan (THF), which
was purchased from Merck.
Sulfonation

PSEBS was sulfonated using CSA. Weighed PSEBS polymer was dissolved in the
, chloroform solvent, then TBP followed by CSA were added dropwise with vigorous stirring.

Degre~ of Sulfonation
The degree'of sulfonation of the prepared Sulfonated.PSEBS (S-PSEBS)was determined
by elemental analysis. The elemental analyzer was used to find out the percentage of
carbon, hydrogen and sulfur. Sulfonation ofPSEBS was found to be uniform throughout.
The degreeof sulfonation increaseswith the increasein the concentration of the sulfonating
agent.
58 The Icfai University Journal of Chemistry, Vol. II, No.2, 2009
Synthesis and Characterization of Fully-Sulfonated PSEBS
for Reference
PSEBS was sulfonated using chlorosulfonic acid at 32°C for over 7 h. The procedures of
sulfonation, purification and membrane preparation have been detailed elsewhere
(Sangeetha, 2004 and 2005). The chemical structure was evaluated using infrared (IR)
spectroscopy. .

Kinetic Measurements by UV-Visible Spectroscopy

Precisely weighed PSEBS (5 g) was dissolved in chloroform (500 mL) in a three-necked
flask with a magnetic stirrer, a thermometer and a drying tube. The solution flask was
placed on an oil bath with a thermostat at a preset temperature. Required amount of
Tri-butyl phosphate (TBP) (to moderate the reaction) followed by CSA were added
dropwisewith continuous stirring. The reaCtionwascarried out in the nitrogen atmosphere.
A solution aliquot (- I mL) was taken from the reaction mixture using a pipette at a
series of set times. These aliquots were quickly transferred into a quam cuvette and the
UV measurement was performed within 1minute. The absorbance became constant after
7 h, correspondingto completesulfonation(X = 1.0).
Sample Analysis and Characterization

UV-visible spectroscopy probes the electronic transitions of molecules as they absorb

light in the UV and visible regions of the electromagnetic spectrum. The UV region
scanned is normally from 200to 400nm. Absorbanceusuallyranges from 0 (no absorption)
to 2 (99% absorption). UV-visible spectra were measured at room temperature using
Systronics UV-visible spectrophotometer 118, in an absorbance mode. The kinetic -
measurement of absorption was performed at 327 nm, which is due to the sulfonated
phenyl ring. The absorbance peak gradually increased with the reaction time and was
recorded as a function of time to follow sulfonation.

Results and Discussion

Degree of Sulfonation
The degree of sulfonation was determined by elemental analysis (Carbone et ai., 2007).
From the sulfur content, the degree of sulfonation was calculated using to the following
equation:
DS= SExlOO
ST ...(2)

where S Eand S T represent experimental and theoretical (assuming one-SO3Hper repeat

unit ofPSEBS) sulfur content of S-PSEBS (Figure 1).The sulfur content and degree of

SulfouarioD Reaction Kinetics of Polystyrene (Ethylene Butylene) Polystyrene 59

sulfonation were found to be increasing with both sulfonating agent
(0.003-0.015 moles/liter) and temperature (0-58 "C), as is evident from Tables I and 2.

Figure 1: Structure of (a) PSEBS; and (b) S-PSEBS

#- I CH.
ClSOaH

H3;-
0
-£m,-~-CBi!-
I
.0 b
[cu,-rr
I~
CHi 9I n
SOaD

Table 1: Degree of Sulfonation ofPSEBS by Elemental Analysis Prepared with

Various Cncentration of Sulfonating Agent
Sl. No. CSA (moleslL) Sulfur (%) Degree of Sulfonation (%)
1. 0.0030 0.883 10
2. 0.0060 1.577 18
3. 0.0090 2.064 24
4. 0.0120 3.360 36
5. 0.0150 4.3% 51
Note: PSEBS - 0.0056 moleslL.

. Table 2: Degree of Sulfonation of PSEBS by Elemental Analysis Prepared

at Various Temperatures
Sl. No. Temperature (°C) Sulfur(%) Degree of Sulfonation (%)
1. 0 4.145 48
2. 15 5.083 59
3. 32 5.390 62
4. 45 5.762 67
5. 58 5.916 69
Note: PSEBS - 0.0056moleslL.

60 The Icfai University Journal of Chemistry, Vol. II, No.2, 2009

Infrared Spectra
By characterizing the polymer samples of both PSEBS and S-PSEBS using infrared
spectroscopy,the followingconclusions can be drawn from the Fourier Transform Infrared
Spectroscopy (FTIR) spectra of Figure 2. Appearance of broad envelope around
3000-3600cm-Iwas assigned to the -OH stretch of sulfonic acid group. Appearance of
pe.akaround 1177em-I, 1054em-I, 1085cm-Iand 1163cm-lwere assigned to the 0 =S=0
(asymmetric stretch), which is due to the presence of SOzstretching confirming the
sulfonation of PSEBS. Disappearance of the peak at the frequency of
720 cm-land 693 em-Ishows that sulfonic acid group is substituted in the aromatic ring,
when compared to the unsulfonated PSEBS. Appearance of the peak at around 869 cm-I
shows that sulfonic acid group is substituted at para position.

Figure 2: FrIR Spectra of (a) Unsulfonated; and (b) S-PSEBS

3500 3000 2500 2000 1500 1000 500

Wavenumber (em-I)
Note: Degree of Sulfonation 25%.

UV Spectra of PSEBS and S-PSEBS

The spectral data of PSEBS showed absorbance at 382 nm, and the S-PSEBS showed
absorbance at 327 nm and 382 nm (Figure 3). The absorption was noted for all the
sulfonated polymer samples at 327nm. The sulfonation progress with respect to increase
in concenuation of the sulfonating agent is clearly reflected in the spectra-gradual
increase in the absorption intensity with the increase in the sulfonation, as shown in
Figure 4.

Sulfonanon Reaction Kinetics of Polystyrene (Ethylene Butylene) Polystyrene 61

 Figure 3: UV Spectra of (a) Sulfonated PSEBS; and (b) Unsulfonated PSEBS

250 300 350 400 450 500 550 600 650 700
Wavelength (nm)
Note: Degree of Sulfonation 25%.

Figure 4: UV Absorbance Curve for Sulfonated PSEBS

1.4

1.2

1.0
u
~~
0.8
~
~
II)
0.6
~
< 0.4
0.2
0
0.00299 0.0059 0.0089 0.0119 0.01497
Concentration of CSA (moleslL)

The band growth at 327 nm is considered to be suitable for kinetic measure~ents since
the band position in wavelength was constant within a limit (327 + /- 0.5 nm). Thisband
is usable as the reference for sulfonation measurement.

The growth of the 327 nm band was recorded as a function of concentration of

sulfonating agent, time and temperature. The absorption band increases with the increase
in these parameters. Figure 5 shows the absorbance peak of unsulfonated and S-PSEBS
with respect to time. When sulfonation time increases, the absorbance band height also
increases. The increase in band area indicates the increase in sulfonation ofthe PSEBS.
The absorbance was taken for two different temperatures (32°C and 58°C) at different
time intervals.
62 The Icfai University Journal of Chemistry, Vol. II, No.2, 2009
 Figure 5: Kinetics ofPSEBS Sulfonation in Chlorosulfonic Acid
at Room Temperature

0.440 ]
ec:: 0.435 J
0.430 I
~ 0.425
':
ell
0.420
~ ,0.415
~
~
0.410
of 0.405
0
] 0.400
< 0.395
0.390
1 2 3 4 5 6 7 8 9 10
Tnne (h)
The reaction was carried at 32°C to attain the saturation level in the 7tJJ.hour.
The absorbance remains constant beyond 7tJJ. hour, as observed from Figure S.But when
the reaction was conducted at S8°C,the reaction saturated within one hour as shown by
the maximum absorbance (Figure 6). The PSEBS was dissolved in chloroform solvent.
This solution was colorless and the absorbance was measured at 327nm and was found to
be zero (/0 = 0). When sulfonating agent was added, sulfonation started immediately.
The absorbance was recorded at various intervals of time. The absorbance peak increased
with time.

Figure 6: Kinetics ofPSEBS Sulfonation in Chlorosulfonic Acid at 58°C

0.50
0.45 . . . . . . . . .
ec:: 0.40
r-- 0.35
N
I'f'I
... 0.30
to
~ 0.25
U
c::
to
0.20
of
0
0.15
..
-'I 0.10
<
0.05
0
2 3 4 5 6 7 8 9
Time (h)

The band height in an absorbance mode at a time 't' is proponional to the concentration
of S-PSEBS repeat unit (/-/0)' At the end of tbe reaction, the concentration of the

SulfonatiOD Reaction Kinetics of Polystyrene (Ethylene Burylene) Polystyrene 63

unsulfonated PSEBS repeat unit is zero (C = 0). The difference in the band height between
the beginning and the end of the reaction is (I a - 10)(Shibuya and Porter, 1992).

The fractional sulfonation, X, is the ratio of the concentrations of S-PSEBS repeat

unit at a time 't', t (Co- C) to that of the end of the reaction (C), which equals the initial
concentration ofPSEBS repeat unit (Co),X may thus be described as a function of the
concentrations of the un sulfonated PSEBS repeat unit.

x = 1-10 - Co-C
la -10 --c;;- ...(3)

where Coand C represent the concentration of the unsulfonated PSEBS repeat unit at the
beginning of the reaction (t = 0) and that at a time t. X = 0 at the beginning of the
reaction and X = 1 at the end of the reaction.

The Arrhenius plot for the sulfonation of PSEBS is given in Figure 7, which shows
that the reaction followsthe form of the Arrhenius equation over the temperature range of
the study. An activation energy of 3.3kJ/mol ofthe repeating unit was calculated from the
slope obtained from a least-squares fit. The very low value 00.3 kJ/mol when compared
to other reports (Shibuya and Porter, 1994; Swier et al., 2004; and Sangeetha, 200S)
indicates that the sulfonation reaction rate is not greatly influenced by temperature. This
may be attributed to the fact that CSA is more active than other sulfonating agents like
sulfuric acid, acetyl sulfate and benzene sulfonic acid.

Figure 7: Arrhenius Plot of the Rate Constant (K)

2.5

2.3
~
~
0
"j'
2.1

1.9
0 0.0036 0.0034 0.0032 0.0030
liT (K-l)

Note: Ea = 3.3kJ/mole.

64 The Icfai University Journal of Chemistry, Vol. IT, No.2, 2009

Conclusion
Sulfonation kinetics of PSEBS in chlorosulfonic acid has been studied using
UV-visiblespectroscopy.The reaction rate is confirmed to be of the first order with respect
to the concentration ofS-PSEBS repeat unit. The sulfonation reaction followsthe form of
an Arrhenius equation over the temperature range of study (0-58 °C) and the obtained
activation energy (Ea) as obtained from the Arrhenius plot is found to be 3.3 kJ/mol. 0

Acknowledgment: The authors would like to thank the Department of Science and
Technology, India, for funding this project (SRIFTP/CS-33/2005 dated August 11, 2005).

References

1. Akovali G and Ozkan A (1986), "Notes on Modification of Polystyrene by

Sulphonation: Some Properties of Poly (Styrenesulphonic Acid)",Porymer, Vol.27,
pp. 1277-1280.
2. Carbone A, Pedicini R, Sacca A, Gatto I and Passalacqua E (2007), "Composite
S.PEEK Membranes for Medium Temperature Polymer Electrolyte Fuel Cells",
Journal of Power Sources, Vol. 178, No.2, pp. 661-666.

3. Curtin D E, Lousenberg R D, Hendry T J, Tangeman P C and Tisack M E (2004),

''Advanced Materials for Improved PEMFC Performance and Life",]. Power Sources,
Vol. 131, pp. 41-48.

4. Park Y S and Yamazaki Y (2005), "Novel NafionlHydroxy Apatite Composite

Membrane with High Crystallinity and Low Methanol Crossover for DMFC's",
PolymerBulletin, Vol.53, pp. 181-189.

5. Reynolds N M, Stidham H D and Hsu S L (1991),"ASpectroscopic Study of Phase-

Transition Kinetics in Syndiotactic Polystyrene", Macromolecules, Vol. 24,
No.2, pp. 3662-3665.
6. Sangeetha D (2004),"Sulfonated Polystyrene-Block-Poly (Ethylene-Ran-Butylene)-
Block Polystyrene as Polymer Electrolytes for Proton Exchange Membrane Fuel
Cells", InternationalJournalofPlasticsIechnology,Vol.8, pp. 313-321.
7. Sangeetha D (2005), "Conductivity and Solvent Uptake of Proton Exchange
Membrane Based on Polystyrene (Ethylene-Butylene) Polystyrene Triblock
Polymer", European Polymer Journal, Vol. 41, pp. 2644-2652.

8. Shibuya N and Porter R S (1992),"Kinectics of PEEK Sulfonation in Concentrated

Sulfuric Acid", Macromolecules,Vol.25, p. 6495.

SuIfonarion Reaction Kinetics of Polystyrene (Ethylene Butylene) Polystyrene 6S

9. Shibuya N and Porter R S (1994), "A Kinetic Study of Peek Sulfonation in
Concentrated Sulfonic Acid by Ultraviolet-Visible Spectroscopy", Polymer,Vol.35,
pp. 3237.
10. Swier S, Gasa J, Shaw M T and Weiss R A (2004), "Sulfonation Reaction Kinetics of
Poly (Ether Ketone and Ketone) (PEKK) Using a Mixture of Concentrater and
Fuming Sulfuric Acid", Ind. Eng. Chern. Res., Vol. 43, p. 6948.

11. Weiss R A and Sen A (1991), "Block Copolymer Ionomers: 1. Synthesis and Physical
Properties of Sulphonated Poly (Styrene-EthylenelButylene-Styrene)", Polymer,
Vol. 32, pp. 1867-1874.

Referena # 65J-2009-06-05-01

66 ,The Icfai University Journal of Chemistry, Vol. n, No.2, 2009