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Acta Materialia 56 (2008) 47804788

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Sulfonation of vulcanized ethylenepropylenediene

terpolymer membranes
F. Barroso-Bujans a,*, R. Verdejo a, A. Lozano a, J.L.G. Fierro b, M.A. Lopez-Manchado a
a
b

Instituto de Ciencia y Tecnologa de Polmeros, CSIC, Juan de la Cierva 3, 28006 Madrid, Spain
Instituto de Catalisis y Petroleoqumica, CSIC, Marie Curie 2, Cantoblanco, 28049 Madrid, Spain
Received 4 February 2008; received in revised form 22 April 2008; accepted 20 May 2008
Available online 21 June 2008

Abstract
In the present work, sulfonation of previously vulcanized ethylene propylene diene terpolymer (EPDM) membranes was developed in
a swelling solvent with acetyl sulfate. This procedure avoids the need to pre-dissolve the raw polymer. The reaction conditions were optimized in terms of solvent type, reaction time, acetyl sulfate concentration and lm thickness to obtain the maximum degree of sulfonation of the polymer. The sulfonation procedure presented in this study yields a degree of sulfonation comparable to the chlorosulfonic
acid procedure. Sulfonic acid groups were detected by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy,
and quantied by titrations. Proton conductivity and water uptake were measured by means of impedance spectroscopy and swelling
measurements, respectively, and were correlated with the degree of sulfonation. Tensile strength and Youngs modulus of sulfonated
EPDM increased with the degree of sulfonation, while elongation at break remained constant. Thermal stability of the sulfonated EPDM
was studied by simultaneous thermogravimetrymass spectroscopy.
2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Sulfonation; Elastomeric polymer; X-ray photoelectron spectroscopy; Mechanical properties; Decomposition

1. Introduction
Ethylenepropylenediene terpolymer rubber (EPDM)
is a cheap and commercially available elastomer with
proved proton conductivity in the sulfonated form [1,2].
The sulfonation procedure of EPDM has been undertaken
with both chlorosulfonic acid and acetyl sulfate. Chlorosulfonic acid is very reactive, producing a highly sulfonated
EPDM with 1.6 mequiv of sulfonic groups per g of EPDM
when a vulcanized EPDM membrane reacts in a heterogeneous medium in dichloroethane [3]. Nevertheless, this
reaction produces a material with limited mechanical properties as the rubber loses its elastomeric characteristics,
becoming a rigid and fragile sulfonated EPDM. Chlorosulfonic acid induces polymer chain cleavage during sulfonation whereas no polymer degradation is observed with
*

Corresponding author. Tel.: +34 915622900; fax: +34 915644853.

E-mail address: fbarroso@ictp.csic.es (F. Barroso-Bujans).

the milder acetyl sulfate [4]. Makowski found that the reaction of EPDM with acetyl sulfate in a homogeneous medium, e.g., dissolving EPDM in heptane, produced a degree
of sulfonation of 0.42 mequiv g1 [5]. This methodology
has been commonly used to obtain sulfonated EPDM
[1,6,7]. However, this procedure is not feasible at industrial
level since it requires an initial dissolution of the polymer,
which is reached after 24 h. Furthermore, following the
Makowski recipe, we observed that a precipitate with an
intense and heterogeneous purple colour was developed.
The resulting material was not possible to process in the
solid-state, essential step in the rubber technology.
In the present report, we develop a new methodology to
obtain a mild sulfonated EPDM with acetyl sulfate on a
previously vulcanized EPDM. This procedure will lead to
important advantages from the technological and environmental viewpoints, since the pre-dissolution of the polymer
is avoided. Here, the eect of the reaction conditions, swelling solvent, reaction time, acetyl sulfate concentration and

1359-6454/$34.00 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2008.05.032

F. Barroso-Bujans et al. / Acta Materialia 56 (2008) 47804788

lm thickness on the extent of grafting onto EPDM are

evaluated. The mechanical, optical and thermal properties
as well as the proton conductivity of the sulfonated samples
are also evaluated.
2. Experimental
2.1. Materials
EPDM terpolymer was supplied by ExxonMobil Chemical under the trade name Vistalon 9500 containing
60 wt.% of ethylene and 11 wt.% of ethylidene norbornene
and a Mooney viscosity ML (1+4) at 125 C of 72. Dicumyl peroxide was purchased from Sigma Aldrich and used as
crosslinking agent. Acetic anhydride (Prolabo) was distilled
prior to use. 1,2-Dicholorethane (Riedel de Haen), cyclohexane (Panreac) and sulfuric acid (oleum) (Riedel de
Haen) were used as received. Tetrahydrofuran (THF)
(Scharlau) was dried with activated Molecular Sieves 4A
(Scharlau) before use.
2.2. Membrane preparation
Rubber compounds with 2 phr (part per hundred rubber) of peroxide were prepared in a Brabender rheometer
at room temperature for 10 min. Vulcanized membranes
of suitable thickness (1 mm for sulfonation experiments
and 0.2 mm for mechanical testing and proton conductivity
measurements) were manufactured at 160 C by compression moulding at the optimum cured time (t95) of 41 min,
which was previously obtained from the curing curves measured in a Rubber Process Analyser (RPA 2000, Alpha
Technologies).
2.3. Sulfonation reaction
Vulcanized EPDM membranes were functionalized with
acetyl sulfate in heterogeneous phase. First, EPDM disk
membranes (thickness = 1 mm, diameter = 29 mm, mass =
0.6 g) were placed in 16 ml of THF, 1,2 dichloroethane or
cyclohexane for 24 h. Acetyl sulfate was freshly prepared
prior to its use. Briey, 7.6 ml (8.1  102 mol) of acetic
anhydride was placed in an iceCaCl2 mixture bath and
cooled to 10 C. Then 2.7 ml (5.3  102 mol) of sulfuric
acid was slowly added to the acetic anhydride, taking care
to ensure that the temperature did not exceed 0 C. After
10 min the viscous liquid was warmed to 10 C. Next,
the corresponding aliquots were taken for sulfonation
(expressed as mmol of acetyl sulfate per g of EPDM) and

4781

added to the solvent containing the swollen EPDM membranes. Detailed sulfonation conditions are given in Table
1. The reactions were stopped by adding ethanol to the
solution. Films were then thoroughly washed by submerging in ethanol for 24 h, changing the ethanol several times.
Finally, membranes were vacuum dried at room temperature for 24 h to constant weight. Sulfonation of 0.2 mm
thick lms was carried out using the same acetyl sulfate
concentration/polymer mass ratio as for the 1 mm thick
lms.
2.4. Analysis of sulfonated EPDM samples
The degree of sulfonation of EPDM, expressed as the
ion exchange capacity (IEC, in mequiv of SO3H per g of
EPDM), was measured by titration as follows: the
membranes were placed in 50 ml of 1 M NaCl for 3 days.
The protons delivered in the reaction RSO3H + Na+ ?
RSO3Na + H+ were potentiometrically titrated using
0.01 M NaOH, which was previously standardized with
0.1 N oxalic acid.
Water uptake and swelling degree (SD) in organic solvents (THF, cyclohexane and dichloroethane) of the
EPDM samples were measured by immersing the disks into
deionized water or in the corresponding solvent at 30 C
for 24 h. The supercial solvent was removed and the samples were immediately weighed. The water uptake and the
SD were calculated as follows:
Water uptake and SD %

WsWd
 100
Wd

where Ws and Wd are the weight of the swollen and dry

sample, respectively.
X-ray photoelectron spectroscopy (XPS) spectra were
recorded using an Escalab 200R spectrometer with a hemispherical analyzer, operated on a constant pass energy
mode and non-monochromatized Mg Ka X-ray radiation
(ht = 1253.6 eV) at 10 mA and 12 kV. Data processing
was performed with the XPS peak program. The spectra
were decomposed by the least squares tting routine using
a Gauss/Lorentz product function after subtracting a Shirley background.
Fourier transform infrared spectroscopy (FTIR) spectra
were recorded using an attenuated total reectance (ATR)
MaxTM II accessory from Pike Technologies on a Perkin
Elmer Spectrum One FTIR spectrometer.
Ultravioletvisible (UVvis) transmittance spectra of
EPDM membranes (1 mm thickness) were recorded in a
Perkin Elmer Lambda 35 UV/Vis Spectrometer.

Table 1
Sulfonation conditions of EPDM membranes

a
b
c
d

(mmol g1 of EPDM)

Reaction time (h)

Cacetyl

1
1
1, 3, 5, 24, 48 and 72
1, 3, 5, 15, 24, 48 and 72

4.2
2.2, 3.7, 5.1 and 6.7
2.2
6.7

sulfate

Swelling solvent
THF, THF + 0.3% of water, cyclohexane and dichloroethane
Dichloroethane
Dichloroethane
Dichloroethane

4782

F. Barroso-Bujans et al. / Acta Materialia 56 (2008) 47804788

about 50% of the chemical crosslinks preferentially occur

via the addition route. Therefore, there should be a further
50% of the olenic groups available for subsequent reactions. Hence, taking this result into account, we selected
the EPDM with the highest ENB percentage commercially
available, to ensure a high degree of sulfonation.
In order to optimize the sulfonation reaction of vulcanized EPDM, four parameters were subjected to study:
swelling solvent, concentration of acetyl sulfate, reaction
time and lm thickness.

Tensile tests were performed at room temperature on an

MTS dynamometer Synergie 200 model, at a crosshead
speed of 200 mm min1, according to ASTM D412 standard specications. The results were the average of at least
four measurements.
EPDM samples were heated from 50 to 800 C, at a
heating rate of 5 C min1 under a constant He ow of
90 ml min1, with a thermogravimetric analyzer (TGA)
Q500 TA Instruments coupled to a Pfeier Vacuum ThermoStarTM mass spectrometer. The weight loss was measured as a function of temperature, and the evolved gas
masses were directly monitored.
The proton resistance was measured by impedance spectroscopy at 25 C using an Autolab analyzer with voltage
amplitudes of 0.1 V AC and 0 V DC. The frequency range
was set from 0.05 to 106 Hz. The proton resistance, R0, is
considered as the modulus of the complex impedance at
the frequency where the phase angle reaches a plateau
(U = 0). Hence, the proton conductivity rp is calculated
as rp = L/R0  A, where A and L are the area and thickness
of the membranes, respectively. Three samples were cut
from dierent regions of the samples and equilibrated with
Milli-Q water for 24 h. The average thickness of wet samples was 0.30 0.04 mm and 6 0.02 mm diameter.

3.1.1. Swelling solvent of vulcanized EPDM

The reaction of the acetyl sulfate, obtained from the
combination of sulfuric acid with acetic anhydride, with
the ENB vinyl groups of EPDM results in the formation
of a vinylic sulfonic acid derivative (Fig. 1) [1].
Vulcanized elastomers are not soluble in any solvent
but swell once introduced into specic solvents. EPDM
samples were swelled in THF, cyclohexane and dichloroethane (Table 1a), reaching the swelling degrees reported
in Table 2. The results show a direct relationship between
the swelling degree and the concentration of sulfonic
groups, with the highest values achieved in dichloroethane. This result is due to a higher mobility of the reactant
through the channels of the elastomeric network opened
by the solvent. Similar results were conrmed by elemental analysis, estimated by an increase in the IEC values.
However, since determinations of sulfur by elemental
analysis are within the error limit of the equipment, subsequent IEC calculations were done by potentiometry.
The existence of sulfonic groups anchored to EPDM
was conrmed by FTIR spectra. FTIR spectrum of the sul-

3. Results and discussion

3.1. Sulfonation reaction
Vulcanization of commercial EPDM rubbers is achieved
by the presence of low levels of olenic functionalities. The
diene monomer 5-ethylidene-2-norbornene (ENB) is introduced to the rubber by reacting one of the olenic sites,
leaving the second one available for further chemical modication such as vulcanization or sulfonation. Peroxide
crosslinking of EPDM is initiated by temperature-induced
decomposition of the peroxide into highly reactive radicals,
which abstract a H-atom from the polymer-forming
EPDM macroradicals. Thus, the crosslinking density of
peroxide-crosslinked EPDM depends on two contributions: the addition of a macroradical to a diene comonomer
and the combination of two EPDM macroradicals. Orza et
al. [8] demonstrated by solid-state nuclear magnetic resonance experiments that in an EPDM with 2% of ENB
O O

1) H2SO4 + CH3COCCH3

Titration

Elemental analysis

IEC
(mequiv g1)

IEC
(mequiv g1)

S
(wt.%)

16
22
45

0.010
0.036
0.090

0.047
0.056
0.140

0.15
0.18
0.45

CH3COSO3H + CH3COOH

CH3

2) (CH2-CH2)0.60-(CH2-CH)0.29

THF
Cyclohexane
Dichloroethane

Swelling
degree (%)

- 10C

Table 2
Sulfonation degree of EPDM samples reached after sulfonation reaction
(used solvents listed in rst column), calculated by titration and elemental
analysis, and swelling degree of EPDM in the corresponding solvents

O
0.11

CH3COSO3H

room
temperature

CH3
(CH2-CH2)0.60-(CH2-CH)0.29

O
0.11

HC

C
CH3

HO3S

Fig. 1. Reaction scheme for (1) the formation of acetyl sulfate and (2) the sulfonation of EPDM.

CH3

CH3COH

F. Barroso-Bujans et al. / Acta Materialia 56 (2008) 47804788

1704

cyclohexane

168

169

170

171

172

173

174

Fig. 3. S2p core-level XPS spectrum of sulfonated EPDM. Sulfonation

reactions were carried out in dierent solvents.

of 1 h and the degree of sulfonation was analyzed by titration. Fig. 4 shows the evolution of the concentration of sulfonic groups as a function of the concentration of acetyl
sulfate. The results suggest that a conversion plateau is
reached, obtaining a maximum degree of sulfonation of
0.16 mequiv g1. As expected, this degree of sulfonation
has a direct eect on the water uptake of the membranes,
which reached a maximum of 7%. Obviously, the water
uptake will have a clear eect on the conductivity measurements as commented below.
3.1.3. Reaction time
In order to analyze the eect of the reaction time on the
degree of sulfonation of EPDM, two concentrations of
acetyl sulfate were used, 2.2 and 6.7 mmol g1, and the reactions were stopped at dierent times (Table 1c and d). Fig. 5
shows that degree of sulfonation increased gradually with
8
0.18
7
0.15

0.12

0.09

4
3

0.06
2
0.03

0.00

0
0

1161 1033

4000

167

3500

3000

2500

2000

1500

1000

Wave number (cm-1 )

Fig. 2. FTIR-ATR spectra of EPDM and sulfonated EPDM membranes.
New absorption bands in sulfonated EPDM are indicated.

water uptake (%)

sulfonated EPDM

THF

BE(eV)

IEC(mequiv/g of EPDM)

Intensity (a.u.)

3424

THF + 0.3% of water

166

3.1.2. Concentration of acetyl sulfate

Concentrations of acetyl sulfate were varied from 2.2 to
6.7 mmol g1 of polymer (Table 1b) at a xed reaction time
EPDM

dichloroethane

S 2p

counts per second (au)

fonated EPDM membrane showed four absorption bands

absent in the spectrum of unmodied EPDM (Fig. 2).
According to the literature [2], those bands are assigned
as: 3424 cm1 (mOH from SO3H groups), 1704 cm1 (H
OH deformation mode of physically adsorbed molecular
water), 1161 cm1 (maO=S=O) and 1033 cm1 (msO=S=O).
Even in dry samples, a band associated with water was
observed due to the presence of highly ionic groups, which
easily absorb moisture. When dry sulfonated EPDM samples are exposed to air, a plasticant eect of water is
observed, i.e. the rigid dry samples become exible in a
short period of time.
The presence of water in the solvent may lead to the formation of sulfate groups [5], but neither XPS nor FTIR
spectra allow distinguish between sulfonic and sulfate signals. This lack of evidence has been also reported by Bashir
et al. [6]. Therefore, sulfonation was carried out in the presence of a known amount of water (0.3%) contained in THF
using the previous procedure. Then, XPS spectra of sulfonated EPDM in dry and wet THF were recorded and compared with those of sulfonated EPDM in dichloroethane
and cyclohexane (Fig. 3). In the four cases, the S2p peak
was t into the spin-orbit S2p3/2 and S2p1/2 components
and a binding energy of the most intense S2p3/2 component
of 169.1 eV was found. These signals are attributed to sulfonic acid groups and sulfate groups, which as stated above
cannot be resolved. Nevertheless, a shift of 0.3 eV of the
non-deconvoluted peak was found in the sample obtained
in wet THF. This result indicates a more electron-withdrawing environment around the S-atom, very likely by
coordination of a water molecule on the polar SO3H
group. Indeed, this sample also displayed a long tail in
the O1s prole (data not shown) extending at binding energies up to 535.5 eV, where the binding energy of O1s corelevel of molecular water usually appears.

4783

cacetyl sulfate (mmol/g of EPDM)

Fig. 4. Concentration of sulfonic groups of EPDM and water uptake of
the samples as a function of the concentration of acetyl sulfate in the feed.
Reaction time = 1 h. Error bars on CSO3 H represent the experimental error
of both volume and mass used in the potentiometric titrations, which were
subsequently used to calculate the sulfonic acid concentrations. Error bars
on the water uptake also represent the experimental error associated with
the dried and wet masses of EPDM.

4784

F. Barroso-Bujans et al. / Acta Materialia 56 (2008) 47804788

Cacetyl sulfate = 2.2 mmol / g

0.7

24

Cacetyl sulfate = 6.7 mmol / g

40

1.2

35

16
0.4
12
0.3
8

0.2

Cacetyl sulfate = 2.2 mmol / g

0.1

10

20

30

40

50

60

70

0
80

3.1.4. Film thickness

Film thicknesses were chosen according to the designed
experiment. For instance, in order to obtain reproducible
and detectable amounts of HCl in titrations, the dimensions
of samples were selected to maximize their weight and the
area of exposed surface lying at the bottom of a round bottom ask. Therefore, round samples of 1 mm thickness,
29 mm diameter and 0.6 g weight were chosen. However,
thinner lms are more suitable to measure the proton conductivity and to prepare the test pieces for mechanical properties. Therefore, 0.2 mm thickness was chosen.
We found that the amount of sulfonic groups in the
EPDM depends on thickness (Fig. 6), suggesting a gradual
sulfonation towards the middle of the sample. The amount
of sulfonic groups obtained in the optimal reaction conditions increases from 0.6 (1 mm thickness) to 1.1 mmol g1
(0.2 mm thickness), comparable to 1.6 mmol g1 obtained
by the chlorosulfonic acid method [3]. Water uptake also
increased to about 30%.

15

Pendant sulfonic acid groups have an important eect

on the properties of EPDM membranes, aecting their
optical, mechanical and thermal properties, as well as their
proton conductivity.

10

1h

0.2

0.4

0.6

0.8

0
1.2

1.0

thickness (mm)
Fig. 6. Dependence of the concentration of sulfonic acid groups with lm
thickness. Samples sulfonated for 1 and 24 h. Error bars on CSO3 H
represent the experimental error of both volume and mass used in the
potentiometric titrations, which were subsequently used to calculate the
sulfonic acid concentrations. Error bars on the water uptake also represent
the experimental error associated with the dried and wet masses of EPDM.

Thus, optical properties of the membranes vary with the

degree of sulfonation of sulfonated EPDM samples, changing from a transparent to an opaque material (Fig. 7).
UVvis transmittance spectra show this transition from

70
0

60
50

0.08 mmol/g

40
30
20
0.17 mmol/g

10

0.37 mmol/g

0
300

3.2. Properties of sulfonated EPDM membranes

20

0.4

Transmittance (%)

the reaction time up to 2430 h, where a conversion plateau

was reached independently of the acetyl sulfate concentration. Possibly, acetyl sulfate could progressively decompose
not being able to react with EPDM. Maximum sulfonic
group concentrations of 0.4 and 0.6 mequiv g1 were
obtained by using 2.2 and 6.7 mmol (acetyl sulfate) g1,
respectively. These membranes had maximum water retentions of 14% and 22%, respectively.

24 h
0.6

0.0
0.0

t(h)
Fig. 5. Concentration of sulfonic groups of EPDM and water uptake of
the samples as a function of the reaction time. Cacetyl sulfate = 2.2 and
6.7 mmol g1. Error bars on CSO3 H represent the experimental error of
both volume and mass used in the potentiometric titrations, which were
used to calculate the sulfonic acid concentrations. Error bars on the water
uptake also represent the experimental error associated with the dried and
wet masses of EPDM.

25
0.8

0.2

Cacetyl sulfate = 6.7 mmol / g

0.0

30

1.0

Water uptake (%)

0.5

IEC (mequiv/g EPDM)

20

water uptake (%)

IEC(mequiv/g of EPDM)

0.6

1.4

400

500

600

700

800

Wavelength (nm)

Fig. 7. (a) Images of EPDM (0 mequiv g1) and sulfonated EPDM with
dierent degree of sulfonations (from 0.08 to 0.37 mequiv g1). (b)
Transmittance of EPDM (0 mequiv g1) and sulfonated EPDM samples
with dierent degree of sulfonations (from 0.08 to 0.37 mequiv g1) in the
UVvis absorption region. Membranes are 1 mm thick.

F. Barroso-Bujans et al. / Acta Materialia 56 (2008) 47804788

the non-modied EPDM with 60% transmittance to the

complete disappearance of transmission for samples above
0.37 mmol (sulfonic groups) g1.
Mechanical properties of EPDM membranes as a function of sulfonic groups are presented in Fig. 8. The ultimate
tensile strength and Youngs modulus was found to increase

4785

with increasing degree of sulfonation, from 2.4 0.4 and

4 0 MPa for non-modied EPDM to 11.8 2.5 and
25 1 MPa for 1.1 mequiv g1 sulfonated membrane, respectively. Hence, the sulfonation reaction on EPDM yields
a more rigid and tough material without adversely aecting
the intrinsic elastic nature of the membranes. In contrast,

Strain
at break (%)

160
140
120
100
80

Stength
Young's
at break (MPa) Modulus (MPa)

60
20
10
0
12
8
4
0
0.0

0.2

0.4

0.6

0.8

1.0

1.2

IEC (mequiv / g of EPDM)

Fig. 8. Mechanical properties (stress at break, strain at break and Youngs modulus) of sulfonated EPDM as a function of the degree of sulfonation. Error
bars indicate the standard deviation of four measurements.

Weight (%)

100

80
60

m/z

40
20

26
27
29
39
41
42
43
48
54
55
56
57
64
66

st

1 derivative

Ion Current (nA)

0.02

0.01

b
Ion Current (nA)

0
0.03

0.01

1E-3

1E-4
350

400

450

500

550

T(C)

0.00
0.6

18
28
44

0.4

0.2

0.0
100

200

300

400

500

600

700

800

T(C)

Fig. 9. TGAMS proles of EPDM: (a) TGA and dTGA. Mass spectrogram for (b) C2 H
x (m/z = 26, 27, 29), C3 Hx (m/z = 39, 41, 42, 43), SO (m/z = 48),

C4 Hx (m/z = 54, 55, 56, 57), SO2 (m/z = 64) and cyclopentadiene (m/z = 66) (note that the enlarged zone is in y-axe logarithmic scale); (c) H2O (m/z = 18),
CO (m/z = 28) and CO2 (m/z = 44).

4786

F. Barroso-Bujans et al. / Acta Materialia 56 (2008) 47804788

previous results on sulfonated EPDM membranes with

chlorosulfonic acid showed a considerable reduction of
their elongation at break to 16% [3]. This improved behaviour may be due to a structural change in the elastomeric
network by the formation of additional crosslinks of ionic
character.
The thermal degradation of non-modied and sulfonated EPDM was carried out by TGAmass spectrometry
(TGAMS) (Figs. 9 and 10, respectively). A rich evolved
gas composition along with their degradation temperature
was detected for both samples. Thermogram of non-modied EPDM showed only one decomposition step between
440 and 471 C, which is attributed to the structural degradation of the polymer backbone. In the highly ionized
atmosphere, volatile products like H2O (m/z = 18), CO
(m/z = 28), CO2 (m/z = 44), C2 H
x (m/z = 26, 27, 28, 29),

C3 H
x (m/z = 39, 41, 42, 43) and C4 Hx (m/z = 54, 55, 56,
57) were identied. Signals with m/z = 28, 42, 54, and
their respective ionizated masses, indicate that the depolymerization of EPDM occurred by releasing ethene (C2H4,

80

60
40
20
0
0.06
0.04

st

1 derivative

b
Ion Current (nA)

Weight (%)

100

0.02

m/z
26
27
29
48
64
66

0.01

1E-3

1E-4
100 200 300 400 500 600
T (C)

Ion Current (nA)

0.00
0.09

c
39
41
42
43

0.06
0.03
0.00
0.03

54
55
56
57

0.02
0.01
0.00
0.6

18
28
44

0.4
0.2
0.0
100

200

300

400

500

600

700

800

T(C)
Fig. 10. TGA-MS proles of sulfonated EPDM: (a) TGA and dTGA.
Mass spectrogram for (b) C2 H
x (m/z = 26, 27, 29), SO (m/z = 48), SO2
(m/z = 64) and cyclopentadiene (m/z = 66) (note that the enlarged zone is

in y-axe logarithmic scale); (c) C3 H

x (m/z = 39, 41, 42, 43); (d) C4 Hx (m/
z = 54, 55, 56, 57); (e) H2O (m/z = 18), CO (m/z = 28) and CO2 (m/
z = 44).

m/z = 28), propene (C3H6, m/z = 42) and butadiene

(C4H6, m/z = 54). Heavier fragments with m/z = 105, 91,
corresponding to ENB units, as reported earlier [9], were
not possible to measure in our system because of technical
limitations, even though a signal with m/z = 66 arising from
cyclopentadiene was observed. However, during the maximum weight loss phenomenon, m/z = 66 signal showed very
low intensity. On the other hand, the signal with m/z = 28
might be either ethene (C2H4) or CO. EPDM does not contain oxygen in its structure, except that which has been
introduced by the dicumyl peroxide during vulcanization,
so CO and CO2 (which is almost negligible in this experiment) might arise from degradation of the crosslinkings.
Also, a small signal of H2O was recorded in the temperature
range of decomposition of the polymer backbone, which
may be associated, as CO, to some mechanism involving
oxygen atoms introduced by the dicumyl peroxide.
TGAMS proles of sulfonated EPDM dier signicantly from those found on non-modied EPDM. Sulfonated EPDM (IEC = 0.6 mequiv g1) showed an initial
5% weight loss (between 122 and 199 C), a second weight
loss step of 2% (between 335 and 360 C) and a third one of
93% (between 446 and 484 C). Volatile products like H2O
(m/z = 18), CO (m/z = 28), CO2 (m/z = 44), C2 H
x (m/
z = 26, 27, 29), C3 H
(m/z
=
39,
41,
42,
43),
SO
(m/
x
z = 48), C4 H
(m/z
=
54,
55,
56,
57),
SO
(m/z
=
64)
and
2
x
cyclopentadiene (m/z = 66) were identied. As detected
previously by FTIR, sulfonated EPDM contains water
strongly associated to ionic groups. Water associated with
sulfonic acid starts to be released at 122 C. The SO3H
decomposition occurs in a broad region of temperature,
showing two maxima (Fig. 10b), one at 175 C and the second at 435 C. The SO3H decomposition of sulfonic
groups seems to be involved in a more complex mechanism
whereby depolymerization into ethene, propene, butadiene
and cyclopentadiene moieties occurs at a lower temperature than in non-modied EPDM (ethene, propene and
butadiene: peak maximum at 345 C; cyclopentadiene:
peak maximum at 175 C).
The degradation of EPDM is complex because thermolysis of the main chain along with degradation of the norbornene moiety can take place at the same time or in a
consecutive process. Regarding the norbornene part, the
main degradation can be associated with a retro Diels
Alder reaction giving a butadiene molecule, which undergoes subsequently degradation at temperatures above
400 C. The remaining part, an unstable cyclopentane moiety, suers a breakdown in several species that include
cyclopentadiene (Fig. 11). In the case of sulfonated EPDM,
the depolymerization anticipates to that of EPDM starting
at about 100 C and produces the same CxHy species than
EPDM. This result indicates that sulfonic groups mediate
in the rupture of polymer backbone, accelerating its
decomposition. Thus, the sulfonic group loss follows two
routes: the rst leads to a desulfonation reaction, which
gives EPDM, whilst the second forms a radical on the norbornene moiety (Fig. 12), which leads to its destabilization,

F. Barroso-Bujans et al. / Acta Materialia 56 (2008) 47804788

heating

4787

C x Hy

+ C x Hy

+ Degradation of main chain

Fig. 11. Decomposition products of EPDM under heating.

SO3H

CxHy

Degradation of main chain

Fig. 12. Unstabilization of ENB moiety after sulfonic group releasing under heating of sulfonated EPDM.

thereby lessening the thermal stability. Further studies of

this mechanism, including a computational study, are being
carried out and will be published elsewhere.
Additionally, the proton conductivity was evaluated as a
function of degree of sulfonation (Fig. 13). The proton
conductivity increases linearly, on a semi-logarithmic scale,
with the degree of sulfonation reaching a maximum of
3.8  103 S cm1. This result is due to the presence of
water in the material as the ionic transport is facilitated
through the interconnected ionic network provided by the
water molecules [10,11]. Owing to these results, we are able
to state that, by changing the reaction conditions of the sulfonation procedure, it is possible to obtain dierent and
well characterized materials. Moreover, if we are able to

1
0.1
0.01

nd the optimum conditions of sulfonation, high conductivity and water uptake can be achieved.
4. Conclusions
A new approach for the sulfonation of a previously vulcanized EPDM has been developed which could positively
implicate on industrial processing. The extent of reaction
depends on several conditions which were optimized. Thus,
a maximum degree of sulfonation of 1.1 mequiv of sulfonic
groups per g of EPDM was attained in 0.2 mm EPDM
lms, using dichloroethane as the swelling solvent, 24 h
of reaction and 6.7 mmol of acetyl sulfate per g of EPDM.
The mechanical properties, tensile strength and Youngs
modulus of sulfonated EPDM increased 56 times compared to the non-sulfonated one, while elongation at break
did not change. The thermal stability of sulfonated EPDM
is decreased by the presence of sulfonic groups in the polymer backbone, which induces cleavage of the polymer at a
lower temperature than EPDM.

1E-3

Acknowledgements

(S/cm)

1E-4
1E-5

The authors of this study gratefully acknowledge the

nancial support of the Ministry of Science and Technology (MCYT, Spain) through its project MAT 200761116. F.B.-B. thanks the Ministerio de Educacion y Ciencia (MEC, Spain) for the mobility program. R.V. acknowledges a Juan de la Cierva contract from the MCYT.

1E-6
1E-7
1E-8
1E-9
1E-10
1E-11
0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

IEC (mequiv/g EPDM)

Fig. 13. Proton conductivity as a function the concentration of sulfonic
groups. The standard deviation for each set of samples was 10%.

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