Journal of Chemical Engineering of Japan, Vol. 53, No. 11, pp.

713–721, 2020 Research Paper

Sulfonated Fluorocarbon Polymers as Proton Exchange

Membranes for Fuel Cells
Yue Zhao2 and Rong Liu1
1
Renmin University of China, No. 59 Zhongguancun Street, Haidian District, Beijing 100872, P.R. China
2
Department of Environmental and Chemical Engineering, Tangshan University,
No. 38, Huayan North Road, Lubei District, Tangshan 063000, P.R. China

Keywords: Sulfonated Fluorinated Block Polymers, RAFT Polymerization, Proton Exchange Membrane, Fuel Cells

Novel diblock copolymers, based on sulfonated hydrophilic-hydrophobic blocks, were synthesized and investigated for
their application as proton exchange membranes. A series of sulfonated poly (1H,1H-Penta fluoro n-propyl acrylate)-b-
poly(benzenesulfonic acid) copolymers (P(PFPA)-b-P(BSFA)) with various fluorinated block lengths were synthesized
via the reversible addition–fragmentation chain-transfer (RAFT) process, and the ethyl group on the sulfonic structure
underwent hydrolysis in hot water. The copolymers came to tough membranes through solvent casting, the performance
and structural property relationships of these materials were studied, the sequence of diblock copolymers was sup-
ported by NMR tests, and GPC demonstrated the low PDI values. Proton conductivity measurements revealed that the
proton conductivity improved with the increasing ratio of hydrophilic and hydrophobic block lengths, and the proton
exchange membranes (PEMs) are beneficial in trans-plane conductivities. The copolymers exhibited higher strain–stress
values along with the ability of greater water uptakes than Nafion. They also depicted better proton conductivities in
liquid water as well as under partially hydrated conditions at 80°C. The new materials are good candidates for use in PEM
systems.

nanostructures, a membrane with high proton conductivity

Introduction
Hydrogen is an excellent alternative to petroleum fuel
(Varcoe et al., 2014), Proton exchange membrane fuel cell
(PEMFC) is an important equipment for the conversion of
hydrogen energy; it can directly convert hydrogen energy
into electric energy, while being eco-friendly and producing
less pollution (Ran et al., 2017). Proton exchange membrane
(PEM) is the key component of PEMFC, and it has been
widely studied by many researchers. However, most of the
synthetic material cannot satisfy the requirements of its
application (Strathmann et al., 2013). Nafion is the current
most widely used PEM, produced by DuPont Int; its hydro-
philic sulfonic acid groups and hydrophobic framework can
form a phase separation in the membrane and improve the
proton conductivity (Bauer et al., 2005). However, Nafion
has many disadvantages, such as high cost, high tempera-
ture resistance, and poor performance under low humidity
(Elabd and Hickner, 2011; Park et al., 2011). It is important
to deterimine alternative materials for Nafion, and several
studies have examined such new alternative materials (Zlo-
torowicz et al., 2017; Vincent and Bessarabov, 2018).
Proton conductivity is the most important performance
parameter of PEMs; it is also an important factor affecting
the performance of PEMFC (Kreuer et al., 2004). By con-
trolling the polymer morphologies and adjusting the ionic
Received on March 3, 2020; accepted on July 2, 2020
DOI: 10.1252/jcej.19we219
Correspondence concerning this article should be addressed to R. Liu
(E-mail address: wendaorong@163.com).
and moderate IEC values can be obtained (Mineart et al.,
2015). Accordingly, various approaches have been report-
ed, such as cross-linking the structure to PEMs, organic-
inorganic hybrid, and polymer sulfonic group modification;
among them, sulfonated polymers are the most widely used
as PEMs.
The block polymer used as the PEMs is generally com-
posed of ionic groups that can serve as the electrolyte in the
central component, conducting the proton from the anode
to the cathode, and the other part of the polymer provides
mechanical properties (Gottesfeld et al., 2018).
Recently, several studies (Roy et al, 2009; Li et al., 2012;
Dong et al., 2013) demonstrated that the sulfonated block
copolymers significantly impact the proton conductivities
in a wide range of temperatures and relative humidities. The
proton conductivity of sulfonated polymer is closely related
to the content of sulfonic acid groups (Ziv and Dekel, 2018),
and the hydrophilic domain formed by the sulfonic acid
group is conducive for the transportation of protons in the
membrane (Li et al., 2017; Zheng et al., 2018). Owing to the
amphiphilic sulfonated group, the polymer exhibit phase
segregation for the ionic groups and polymer main chain,
creating a nanoscale morphology of hydrophilic and hydro-
phobic domains for proton transportation. However, to a
certain degree of sulfonation, the PEMs tend to absorb too
much water or even become soluble in water. To avoid this,
a variety of functional block copolymers, consisting of hy-
drophilic and hydrophobic blocks for the PEMs, have been
reported (Hou et al., 2010; Takamuku and Jannasch, 2012;
Kins et al., 2014; Seh et al., 2017). With the formation of ion

Vol. 53  No.©11 

Copyright 2020 
2020
The Society of Chemical Engineers, Japan 713
channel structures, polymers can achieve effective proton
conduction because the hydrophilic sulfonated polymer seg-
ments form an interconnected three-dimensional network
and the hydrophobic segments form a reinforced comple-
mentary network, which can maintain water stability and
enhance the mechanical properties (Roy et al., 2009; Hou et
al, 2010; Li et al., 2012; Takamuku and Jannasch, 2012; Kins
et al., 2014).
It has been demonstrated that perfluorinated sulfonic acid
polymers, such as Nafion, can easily lose water and stop pro-
ton conduction when the temperature is higher than 90°C;
the improvement in the degree of sulfonation can maintain
the proton conductivity at high temperature while it dam-
ages the mechanical properties. Therefore, it is necessary to
develop a PEM that can maintain the proton conductivity
and have the corresponding mechanical properties under
certain temperatures.
Reversible addition–fragmentation chain-transfer (RAFT)
polymerization is a type of reactive and controllable free rad-
ical polymerization (CRP), which was proposed by Rizzardo
in 1998 (Chiefari et al., 1998). It is suitable for a wide range
of monomers and significantly conducive for the polymeriza-
tion of olefin monomers with special functional groups to
prepare block, graft, and star copolymers.
In this paper, we report a novel and versatile method
of forming amphiphilic block copolymers, poly (1H,1H-
Penta fluoro n-propyl acrylate)-b-poly(ethyl styrene sulfo-
nate), using a 2-step approach via RAFT polymerization.
The RAFT agent, 2-dodecylsulfanylthiocarbonylsulfanyl-
2-methyl-propionic acid (DTMPA), was implemented to
polymerize the diblock polymer with the ester moieties as
the functional group; these block copolymers can be em-
ployed as PEMs with the increased conductivities.
1. Experimental
1.1 Materials
Sodium p-styrene sulfonate (25 wt% in H2O, technical
grade, Sigma-Aldrich), 1H,1H-Penta fluoro n-propyl acrylate
(PFPA, Flurochem), and 2,2′-azoisobutyronitrile (AIBN,
Fluka, 98%) were purified via recrystallization from metha-
nol. Ethyl bromide (Sigma-Aldrich), silver nitrate (AgNO3),
toluene, acetonitrile, THF, DMF, DMAc, and 1,4-dioxane
were purchased from chem-supply Pty. Ltd.; DMSO, di-
ethyl ether, and methanol were supplied by Tian Jin Kewei
chemistry Co., Ltd. The RAFT agent DTMPA was prepared
according to the literature (Wang et al., 2019).
2. Synthesis
2.1 Synthesis of ethyl styrene sulfonate (ESS)
Ethyl styrene sulfonate (ESS) was synthesized according
to the work of Woeste (Woeste et al., 1993); AgNO3 (18.7 g,
0.11 mol) was poured dropwise in the aqueous solution of
sodium p-styrenesulfonate (20.6 g, 0.1 mol) in an ice bath
under vigorous stirring for 48 h in the dark environment.
The resulting product was washed by 50 mL deionized water
714
three times and isolated by precipitation in acetonitrile.
After filtration, the solid was co-boiled with 1,4-dioxane 3
times to remove moisture from the system. Styrene silver
was dissolved in acetonitrile and back-flow with ethyl bro-
mide (20 mL, 0.34 mol) for 12 h at 70°C. The products were
dissolved in toluene and dried by reduced pressure distil-
lation. 1H NMR (CDCl3): δ1.31, (t, 3H, J=6.9 Hz, CH3 Et);
4.14 (q, 2H, J=7.2 Hz, O–CH−2 ); 5.48 (d, 2H, J=11.1 Hz,
CH2 vinyl); 5.93 (d, 2H, J=17.7 Hz, CH2 vinyl); 6.81 (dd,
1H, CH vinyl); 7.57 (d, 2H, J=8.4 Hz, CH atom); 7.88 (d,
2H, J=8.4 Hz, CH arom).
2.2 Synthesis of poly(ethyl styrene sulfonate) (PESS) with
RAFT polymerization
ESS (3.7 g, 17.5 mmol), the RAFT agent (64 mg,
0.175 mmol), and initiator AIBN (1.3 mg, 0.053 mmol) were
mixed in THF (12.5 mL) in a glass vial. After degassing with
argon gas, the mixture was put in an ice bath for 20 min, and
then immersed in an oil bath at 65°C for 24 h. The polymer-
ization was terminated by putting the flask in an ice bath for
5 min and introducing air. The aimed polymer was precipi-
tated in diethyl ether and dried under vacuum. The conver-
sion of the monomer was determined by 1H NMR (CDCl3)
from the peaks at δ6.6–6.8 ppm and δ7.4–7.58 ppm, assigned
to the H atom in the benzene ring and δ5.0–5.4 ppm at-
tributed to the terminal double bonds in the allyl acrylate
units. A conversion of 90% was obtained after 20 h, which is
equivalent to 90 repeating units. The GPC demonstrated a
PDI of 1.10.
2.3 Synthesis of block copolymer poly (1H,1H-Penta
fluoro n-propyl acrylate)-b-poly(Benzenesulfonic
acid) P(PFPA)-b-P(BSFA)
The PESS macro-RAFT agent (0.65 g, 0.031 mmol),
PFPA (3.2 g, 15.5 mmol), initiator AIBN (1.66 mg,
1.0×10−3 mmol) were dissolved in the mixed solution with
DMAc (0.2 mL) and THF (1.6 mL) in a glass vial. After de-
gassing by argon, the mixture was heated to 85°C for 24 h
in a dark environment. The resulting solution was separated
from the organic phase with 50 mL hexane and ether (v/v
10 : 1). After drying, a light yellow solid powder was ob-
tained. The diblock copolymer also contained the ethyl pro-
tective group on the sulfonic structure, and the final product
P(PFPA)-b-P(BSFA) was obtained after undergoing hydroly-
sis for 12 h in boiling water.
2.4 Casting film under electric field
The synthesized block copolymer was dissolved in DMSO
to form a 5 wt% casting solution; then, the solution was
poured on a glass plate and dried at 65°C in an oven. The
casting membrane cooled between 2 parallel plates and was
given an electric field in the vertical direction. The effec-
tive value of the electric intensity was 4,500 V/cm−1, with a
sine wave type frequency of 0.1 Hz. After cooling, the mem-
brane above was taken out, immersed in deionized water, and
named E-membrane. Simultaneously, another C-membrane,
created using the same steps without the voltage provided,
Journal of Chemical Engineering of Japan
was used as a control group. A 4 mm metal mash was used as
an upper plate to avoid the influence of evaporation.
3. Analysis
3.1 Nuclear magnetic resonance (NMR) spectroscopy
All NMR spectra were recorded using a Varian UNITY-
plus 400 MHz spectrometer. Deuterated chloroform was
used as the solution for examination.
Gel Permeation Chromatography (GPC). The molecu-
lar weight distributions were determined by GPC with a
Shimadzu modular system having DMF (0.05 M LiBr) at
70°C with a flow rate of 1 mL·min−1. The system incorpo-
rated a DAWN HELEOS LS detector (λ=658 nm), a Shi-
madzu RID-10 refractometer (λ=633 nm), and a Shimadzu
SPD-20 A UV-Vis detector. The system was calibrated from
500 to 106 g/mol with polystyrene as the standard. The poly-
mer (5 mg) was dissolved in 2 mL DMAc, followed by filtra-
tion using a filter with a pore size of 0.22 µm.
Dynamic Light Scattering (DLS). The hydrodynamic di-
ameters (Dh) of the aggregates were determined by a Mal-
vern Zetasizer Nano ZS analyzer. The mean diameter was
calculated by the arithmetic mean using the relative inten-
sity of each particle size. The solution (0.5 g L−1) was filtered
before analysis, and run three times at 25°C.
3.2 Scanning Electron Microscopy (SEM)
Scanning electron microscopy (SEM, PHILIPS XL30
ESEM, U.S.A.) was used to visualize the surface structures of
the membranes. All the membranes were coated with a layer
of gold (Eiko IB-3 ION COATER) before being observed via
SEM.
3.3 Transmission Electron Microscope (TEM)
TF30 transmission electron microscopy (TEM) (Fei Co.,
Eindhoven, the Netherlands) was used to observe the mor-
phology of the samples. The Gatan US1000 2 K×2 K CCD
camera (Pleasanton, CA) was used to take photos. A total
of 1% of the OsO4 ethanol solution was dropped next to the
copper mesh and TEM measurements were performed after
leaving it in a fume hood for 1 h.
3.4 Thermogravimetric analysis (TGA)
The thermal stability of block copolymer was tested by
thermogravimetric analysis (TGA) and different scanning
calorimetry. TGA was performed at temperatures ranging
from the room temperature to 800°C under a dynamic dry
nitrogen atmosphere at a heating rate of 10°C·min−1 using a
PerkinElmer, Inc. Pyris-1 TGA system.
3.5 Measurement of water uptake
The water uptake was determined by gravimetrical. The
membranes were soaked in DI water at 25°C for 2 days, the
wet membranes were removed from the water and quickly
weighed after removing the surface droplets. The water up-
take was calculated according to Eq. (1). Massdry refers to the
mass of the dry membrane and masswet denotes the weight
Vol. 53  No. 11  2020
Fig. 1 Measurement cell for membrane conductivity in the trans-
plane direction. 1–Environmental chamber; 2–lower electrode
(stainless steel); 3–teflon cell; 4–membrane; 5–upper electrode
(stainless steel); 6–FRA
of the wet membrane.
mass wet − massdry
Water uptake (%) = ×100% (1)
massdry
The membrane was cut into a rectangular diaphragm (Sd)
and dried in a vacuum oven at 100°C for 24 h, and then im-
mersed in liquid for 48 h at 25°C. The area of the swollen
film was measured as Sw and the swelling ratio was calculat-
ed by Eq. (2). By changing the liquid temperature, different
swelling ratios can be obtained.
Sw − Sd
swelling ratio (%) = ×100% (2)
Sw
3.6 Mechanical characterization membranes
The tensile stress was calculated according to the Chi-
nese Standard GB-13022-91. The membranes were cut into
rectangles (60 mm×10 mm). The tensile test was performed
using the electronic universal testing machine (WD-10D,
Changchun Second Tester Factory) with a cross-head speed
of 1 mm/min at room temperature.
3.7 Electrical conductivity test
Two electrodes were used to measure the vertical conduc-
tivity. The film between the 2 metal electrodes was used to
form a sandwich structure. The measuring device is illus-
trated in Figure 1. The resistance R of the membrane under
different conditions was measured by the AC frequency
response analyzer (Potentiostat 2273, Prinston, U.S.A.); L
denotes the distance between the 2 electrodes and A is the
cross-section of the film between the electrodes (Eq. (3)).
The electric field strength was 4,500 V·cm−1, with a sine
wave frequency of 0.1 Hz.
L
δ= (3)
R⋅A
4. Results and Discussion
Before synthesizing the di-block copolymers, we used the
ESS monomer to evaluate the suitability and applicability of
the RAFT process for polymerization (Figure 2). The ESS
used in this work contained the sulfonic acid group as the
functional pendant side groups. Soulfonic acid is a fixed ion
715
 Fig. 2 Synthesis of P(BSFA)-b-P(PFPA) via RAFT polymerization

Fig. 3 NMR diagram of Polymer with a fluorinated block and a Benzenesulfonic acid block
(a) PESS homopolymer, (b) PBSFA-P(PFPA) block copolymer

and plays an important part in the membrane conduction
process, when H+ is used as the counter ions, it can dis-
sociate to provide protons (Hou et al., 2011). However, the
sulfonate group is hydrophilic, it can combine with the water
molecules to provide a conducting channel. The synthesis of
the sulfonate polymers was previously reported for different
membrane applications (Ting et al., 2009). Unfortunately,
the approach could not fully satisfy the requirements and the
product did not exhibit any advantages in terms of the me-
chanical behavior or water absorbability (Kim et al., 2018).
The RAFT polymerization process was investigated.
The RAFT agent, 2-dodecylsulfanylthiocarbonylsulfanyl-
2-methyl-propionic acid (DTMPA), was employed as the
reagent for polymerization.
First, the solvent was selected. It should dissolve both the
ESS and DTMPA. Many polar solvents with high boiling
points, such as DMSO and N-methyl pyrrolidone, cannot
efficiently control the RAFT agent. Therefore, THF was se-
lected as the solvent for polymerization, which can dissolve
high concentration ESS and optimally control the RAFT
polymerization process.
After the first step of polymerization, similar reactions
were applied to synthesis the monomer 1H,1H-Penta fluoro
n-propyl acrylate (PFPA). PESS was employed as a mac-
roRAFT agent to initiate the polymerization process. The
reaction temperature (85°C) was set lower than the decom-
position (Pai et al., 2004), it also helps in stabilizing the
group trithiocarbonates (Figure 1). The SEC diagrams of the
homopolymer and block copolymer were inconclusive in
elucidating whether the molecular weight increased linearly
with the conversion; additionally, the PDI values were low.
The results of SEC demonstrated that with the conver-
sion of molecular weight to a high value, the molecular
weight distribution became narrow, the block copolymer
retained the homopolymer, and the reduction in the appear-
ance of peaks can be ascribed to the increased hardness of
the fluorocarbon polymer; moreover, low polydispersities
(PDI) of approximately 1.20 were observed. Furthermore,

716 Journal of Chemical Engineering of Japan

the molecular weight calculation of NMR and SEC were sig- In Figure 6, TEM was used to detect the polymers in the
nificantly consistent before the deprotection step. However, vertical direction with OsO4 staining. In the photos, the
the peak of block copolymer in RI detection was negative, black part represents the area containing the sulfonate ion
indicating variations in the polymer polarities (Figure 3). In group, and the gray white part denotes hydrophobic phase
comparison to standard polystyrene, the fluorocarbon poly- (the highlighted part is blank). By comparing the TEM im-
mers resemble “hard spheres”, which constitutes the bias of ages of polymers with different block ratios, it was found
the RI detector and affects the accurate determination of the that the longer the fluorine-containing block, the easier it is
polymer molecular weight (Matsumoto et al., 2004; Wang to assemble it in a more regular pattern and form a separate
et al., 2018). phase.
Considering the charges on the sulfonate groups of the The thermal stability tests for the block copolymer with
monomer would cause chain transfer or chain termination different P(PFPA) parts were performed via TGA (Figure
in free radical polymerization, thereby destroying the active 7). All membranes were dried at 50°C for three days before
sites or affecting the polymerization products. It is necessary the thermal analysis. For the homopolymers (P(PBSFA)90),
to link an alkane chain to the sulfonic group for protection;
subsequently, the deprotection step was performed to form Table 1 Diblock copolymers P(BSFA)m-P(PFPA)n with different
PPFPA-b-PBSFA. The subsequent reaction for removing the block ratios
protection groups was performed by heating with boiling
Mn a) Mn b) IEC Dh b)
water for 1 h. Attention should be paid during the process m n P.D.I.
[mol/Kg]
of finetuning the conductions to prevent the polymeric [g mol−1] [g mol−1] [nm]
backbone and sulfonate units from degradation, thereby 1 90 396 89,839 88,950 0.93 1.23 14
ensuring the investigation of the ester bond. 1H-NMR 2 90 255 64,459 63,720 1.23 1.21 10
tests (Figure 3) confirmed the disappearance of signals at 3 90 142 44,119 43,480 1.48 1.19 8
δ=1.30 ppm of methyl and the ratio between PFPA and sul- Nafion recast 105–106 1.10
fonate styrene confirmed that the deprotection step did not membrane
destroy the P(PFPA) part or polyBSFA block; additionally, a)
Characterization data by NMR, b) characterization data by Gel Per-
the eater bond was not broken on the block copolymer. meation Chromatography (GPC)
Dynamic light scattering (DLS) was used to detect the
hydrodynamic radius of P(BSFA)90-P(PFPA)n polymers with
different block lengths in water. A slight increase in radius
can be observed as the block length increased (Table 1, Fig-
ure 4). It was observed that P(BSFA)90-P(PFPA)396 has a sig-
nificantly higher hydrodynamic radius, and the PFPA parts
are hydrophobic segments, which would aggregate at the
core in liquid water; according to the data, a large number of
PFPA indicates bigger hydrodynamic diameters.
The surface SEM morphologic examination showed that
the clear folds on the surface of the membrane of polymer
P(BSFA)90-P(PFPA)396 (Figure 5) were gradually formed
during the chemical decay. Considering that the membrane
was tested in a stress-free process, the appearance of the fold
can be attributed to the increased viscosity of the polymer
solutions and the slow volatilization of DMSO; with the
increase in the PFPA repeating units, the hydrophobicity of
Fig. 4 DMF-GPC of the 1st block PBSFA and diblock polymer with
the polymers improved and the smoothness of the polymer
protection group ether
membrane surface became worse.

Fig. 5 SEM of the surfaces of PEMs from polymer with different block ratios
(a) PBSFA90-P(PFPA)142, (b) PBSFA90-P(PFPA)255, (c) PBSFA90-P(PFPA)396

Vol. 53  No. 11  2020 717

Fig. 6 TEM of polymers with different block ratios, stained by OsO4. The dark parts are ionic clusters. (a) PBSFA90-P(PFPA)142, (b) PBSFA90-
P(PFPA)255, (c) PBSFA90-P(PFPA)396
Fig. 7 TGA of diblock copolymer polymers
the onset temperature for the weight loss was observed at
the beginning. However, almost no weight loss was ob-
served between 80 and 285°C, implying that the thermal
stability of the block copolymer was enhanced. For the block
copolymers, the first weight loss step observed in the range
285–325°C was due to the decomposition of the sulfonic
acid groups; the second weight loss steps were around at
400–450°C, indicating the decomposition of the polymer
main chains. However, the more PFPA segments there were
in the block copolymers, the less residual char remained at
the final temperature, indicating that the PFPA blocks, as the
decomposition fragment, affected the thermal stability of
the polymer main chain.
The stress–strain curves for polymeric films were ob-
tained by applying a tensile force at a uniform rate at a
constant temperature. The stress–strain curve profiles were
influenced by the polymer structure, molecular weight, and
distribution of molecular weight (Matsumoto et al., 2004;
Kraytsberg and Ein-Eli, 2014; Verma et al., 2014; Wang
et al., 2018). The curves can also provide data on the break
point and the elongation at break, which are also important
indexes with which to characterize the properties of poly-
mers. Figure 8 shows the tensile strength and elongation-
at-break curves of membranes as received nafion recast,
PBSFA90-P(PFPA)396, PBSFA90-P(PFPA)255, and PBSFA90-
P(PFPA)142. Compared to the nafion recast, the stress-strain
curves of the polymeric membrane showed the same initial
steep slope at relatively low strains; however the stress-strain
behaviors are very different with the different blocks of
718
Fig. 8 Strain–stress curves of membrane materials
fluorocarbons. The membrane P(BSFA)90-P(PFPA)142 broke
at 4.03 Mpa with the strain at 35%, 142 PFPA blocks, and
inner core regions that could not act as crystalline domains
that could maintain their integrity toward external stresses
while improving mechanical properties. For the P(BSFA)90-
P(PFPA)255 membrane, the elongation-at-break increased
to 35% at 5.73 MPa, which indicated that there was a close
connection for 255 PFPA parts in the test of the membrane’s
mechanical properties. A higher degree of PFPA can cause
the membrane elasticity to decline, thereby decreasing the
membrane’s tensile strength, and more brittle membranes
can be expected (Ozmaian and Naghdabadi, 2014; Liang
et al., 2015; Liu et al., 2017) While crystallization would
normally make the polymer hard and brittle, the polymer
PBSFA90-P(PFPA)396 broke at 4.13 MPa, indicating that a
greater number of PFPA block segments caused the lower
intermolecular interaction to cure the curling process of the
polymer chains (Wang et al., 2018). Meanwhile, the highest
stress was 2.35 MPa for recast nafion at a stress of 35%; this
was affected by solvent action and the entanglement of the
molecular chain of recast nafion was different from that of
melt extrusion (Xiao et al., 2015). Hence, it is necessary to
fabricate the PFPA to a degree that keeps the membrane
durable. Compared to this value, the tensile strength of
the P(BSFA)90-P(PFPA)255 membrane has the highest tensile
strength for PEM, and the tensile property of the membrane
is adjustable by the thickness of the polymer layer.
The water uptake of PEMs is one of the most important
properties of the fuel cell, and it is key to the proton con-
Journal of Chemical Engineering of Japan
ductivity and dimensional stability of the PEM. The water
uptake of the membranes was measured at temperatures
ranging between 30–80°C, as 60–80°C is the most desirable
working temperature for PEM fuel cells (Kraytsberg and
Ein-Eli, 2014; Wang et al., 2018).
It is well known that water absorption has an important
influence on proton transport and the mechanical properties
of proton exchange membranes. For most proton-conduc-
tive polymers, sufficient water absorption is necessary to
ensure effective proton transport in the membranes. Water
is a carrier for transporting protons through proton mem-
branes. An appropriate water content is therefore beneficial
to the formation of better transport channels in hydrophilic
regions. The higher the water absorption, the more protons
dissociate, and the greater the proton conductivity becomes.
The variation in the trend of water absorption of dif-
ferent membranes with temperature was given in Figure
9. The data showed that for the water absorption capacity
that is mainly determined by the hydrophilic group in the
molecular structure, the water absorption and swelling ca-
pacity of the nafion recast membrane are similar to those
in the literature (Zawodzinski et al., 1993; Xiao et al., 2015).
With the increase in temperature, the water absorption of
proton membranes increased gradually, particularly for the
P(BSFA)90-P(PFPA)142 copolymer; here, the water absorp-
tion increased from 31.78% at 20°C to 123.26% at 80°C be-
Fig. 9 The ability of water uptake of PEMs with different block
polymers
Vol. 53  No. 11  2020
cause the increase in temperature accelerates the movement
of molecular chains and leads to the increase of transport
channels. This provides more space for water absorption
in the membranes, and at the same temperature, because
the sulfonic groups are hydrophilic groups and the more of
them there are, the more water is absorbed. It the also can be
seen that as the proportion of hydrophobic PFPA fragments
increased, the water absorbed by the polymer P (BSFA)90-
P(PFPA)255 and P(BSFA)90-P(PFPA)396 increased within the
acceptable range of the dimensional stability and long-term
durability of the membrane. The curve in Figure 9 shows
that the swelling ratio of the film increased with the increase
in temperature. For P(BSFA)90-P(PFPA)142 membranes, the
swelling ratio increased from 24.32% at 20°C to 81.44% at
80°C. High degrees of hydration typically lead to high con-
ductivities, cause critical dimensional changes, reduce the
morphological stability of the membranes at a level to which
membrane loses a certain extent of its mechanical strength
and making it impractical for use in a PEM (Liang et al.,
2015; Wang et al., 2018; Wang et al., 2019).
Compared the three different membranes, the water
absorption of the membrane P(BSFA)90-P(PFPA)255 was
12.72% at 30°C and 29.22% at 80°C and its swelling ratio
was 26.73% at 30°C and 43.81% at 80°C; therefore, when
combined with the analysis of mechanic properties, was
chosen as the sample with which to test proton conductivity.
With the ordered self-assembled block copolymer mor-
phology, the P(BSFA)-b-P(PFPA) with the non-swellable ion
block can produce ideal high proton conductivity between 2
electrodes in the electric field. The method was described in
the section on analysis. The effective area of the membrane
is the same as that of the electrode: 0.2827 cm2. After electric
field treatment, the trans-plan conductivity of P(BSFA)90-
P(PFPA)255 was approximately 2.1 times than that with-
out electric field treatment. In contrast, the conductivity in
plane decreased from 7.2×10−2 to 8.2×10−2 S/cm (Figure
10). For most situations, in-plane measurement for the two
block copolymers with layered micro domains are preferen-
tially oriented to the plane of the membrane, resulting in the
improvement of proton conductivity to an order of magni-
tude higher than the trans-plane measurement in terms of
Fig. 10 Conductivities of the diblock copolymers in response to the
trans-plane electric field
719

Fig. 11 Proton conductivity versus relative humidity for polymer
P(BSFA)-P(PFPA)
selectivities (Ozmaian and Naghdabadi, 2014; Liang et al.,
2015; Zhao et al., 2016). As a result, there is no doubt that
trans-plane measurement is more suitable for the operation
of the fuel cell and that proton transport on the thin dimen-
sion of the membrane is most important. Caution should
be taken in this measurement as there must be a sufficient
separation between the trans-plane electrodes to ensure the
bulk resistance of the membrane is greater than other resis-
tances in the system (Zhao et al., 2013; Wang et al., 2014; Ko
et al., 2015).
Figure 11 shows the proton conductivity at 80°C with rel-
ative humidity as a series of P(BSFA)-P(PFPA) copolymers
with the data for the nafion recast shown for comparison.
Here, the performance increases with IEC from 0.93 to 1.48;
in addition, both the P(BSFA)90-P(PFPA)142 with IEC 1.48
and P(BSFA)90-P(PFPA)255 with IEC 1.23 outperformed the
nafion recast. Thus, high conductivity can be achieved by
changing the IEC (Roy et al., 2009; Zhao et al., 2013; Kim
et al., 2018; Wang et al., 2019). Furthermore, as the data
showed, the increase in IEC did not lead to any change in
the water uptake. The materials differed only in terms of
the lengths of the hydrophobic blocks of these three syn-
thesized copolymers, the P(BSFA)90-P(PFPA)142 displayed
highest water uptake, and the P(BSFA)90-P(PFPA)396 showed
much lower water uptake and proton conductivity than the
P(BSFA)90-P(PFPA)255. Therefore, given the structure of the
hydrophobic and hydrophilic blocks, the change in the ratio
of the former does have a substantial effect on its electro-
chemical properties.
Conclusions
The amphiphilic sulfonated–fluorinated block copoly-
mers poly(1H,1H-Penta fluoro n-propyl acrylate)-b-poly-
(Benzenesulfonic acid) were successfully obtained via RAFT
polymerization. The existence of the polymers was sup-
ported by 1H NMR, GPC, and TGA. The boiling water was
selected as the approporiate solvent in the deprotection of
poly(styrene sulfonic ethyl ester), generation of polyBSFA,
and as the next step for the casting of the film used as the
720
PEM. The IEC can be changed simultaneously with changes
in the length of the hydrophobic and hydrophilic blocks.
Furthermore, increasing length of the hydrophobic seg-
ment was found to affect the IEC characteristics and water
absorption. The amphiphilic block polymer P(BSFA)90-
P(PFPA)255 has the most advantages in terms of tension,
water absorption, and proton conductivity; therefore, it
would be possible to use it as a commercial product as it
successfully conducts proton in an electric field.
Acknowledgement
Yue Zhao would like to thank the key research and development
program project of Hebei province, China (No. 17211223), the science
and technology project of Tangshan city, China (No. 17110229a) and
Science and Technology Project of Hebei Education Department, China
(No. Z2020102).
Literature Cited
Bauer, F., S. Denneler and M. Willert-Porada; “Influence of Tempera-
ture and Humidity on the Mechanical Properties of Nafion (R) 117
Polymer Electrolyte Membrane,” J. Polym. Sci., B, Polym. Phys., 43,
786–795 (2005)
Chiefari, J., Y. K. Chong, F. Ercole, J. Krstina, J. Jeffery, T. P. T. Le, R.
T. A. Mayadunne, G. F. Meijs, C. L. Moad, G. Moad, E. Rizzardo
and S. H. Thang; “Living Free-Radical Polymerization by Revers-
ible Addition–Fragmentation Chain Transfer: The RAFT Process,”
Macromolecules, 31, 5559–5562 (1998)
Elabd, Y. A. and M. A. Hickner; “Block Copolymers for Fuel Cells,”
Macromolecules, 44, 1–11 (2011)
Gottesfeld, S., D. R. Dekel, M. Page, C. Bae, Y. S. Yan, P. Zelenay and Y.
S. Kim; “Anion Exchange Membrane Fuel Cells: Current Status and
Remaining Challenges,” J. Power Sources, 375, 170–184 (2018)
Hou, J. B., J. Li and L. A. Madsen; “Anisotropy and Transport in Poly-
(arylene Ether Sulfone) Hydrophilic–Hydrophobic Block Copoly-
mers,” Macromolecules, 43, 347–353 (2010)
Hou, H., M. L. Di Vona and P. Knauth; “Durability of Sulfonated
Aromatic Polymers for Proton-Exchange-Membrane Fuel Cells,”
ChemSusChem, 4, 1526–1536 (2011)
Kim, K., P. Heo, J. Han, J. H. Kim and J. C. Lee; “End-Group Cross-
Linked Sulfonated Poly(arylene Ether Sulfone) via Thiol-Ene Click
Reaction for High-Performance Proton Exchange Membrane,”
J. Power Sources, 401, 20–28 (2018)
Kins, C. F., E. Sengupta, A. Kaltbeitzel, M. Wagner, I. Lieberwirth, H. W.
Spiess and M. R. Hansen; “Morphological Anisotropy and Proton
Conduction in Multiblock Copolyimide Electrolyte Membranes,”
Macromolecules, 47, 2645–2658 (2014)
Ko, T., K. Kim, B. K. Jung, S. H. Cha, S. K. Kim and J. C. Lee;
“Cross-Linked Sulfonated Poly(arylene Ether Sulfone) Membranes
Formed by in Situ Casting and Click Reaction for Applications in
Fuel Cells,” Macromolecules, 48, 1104–1114 (2015)
Kraytsberg, A. and Y. Ein-Eli; “Review of Advanced Materials for Pro-
ton Exchange Membrane Fuel Cells,” Energy Fuels, 28, 7303–7330
(2014)
Kreuer, K. D., S. J. Paddison, E. Spohr and M. Schuster; “Transport
in Proton Conductors for Fuel-Cell Applications: Simulations,
Elementary Reactions, and Phenomenology,” Chem. Rev., 104,
4637–4678 (2004)
Li, N. W., S. Y. Lee, Y. L. Liu, Y. M. Lee and M. D. Guiver; “A New Class
of Highly-Conducting Polymer Electrolyte Membranes: Aromatic
Journal of Chemical Engineering of Japan
 ABA Triblock Copolymers,” Energy Environ. Sci., 5, 5346–5355
(2012)
Li, Z., X. Y. He, Z. Y. Jiang, Y. H. Yin, B. Zhang, G. W. He, H. W. Tong,
H. Wu and K. Jiao; “Enhancing Hydroxide Conductivity and
Stability of Anion Exchange Membrane by Blending Quaternary
Ammonium Functionalized Polymers,” Electrochim. Acta, 240,
486–494 (2017)
Liang, Y., C. L. Gong, Z. G. Qi, H. Li, Z. Y. Wu, Y. K. Zhang, S. J.
Zhang and Y. F. Li; “Intermolecular Ionic Cross-Linked Sulfonated
Poly(ether Ether Ketone) Membranes Containing Diazafluorene
for Direct Methanol Fuel Cell Applications,” J. Power Sources, 284,
86–94 (2015)
Liu, J. C., P. L. Zheng, M. Feng and X. B. Liu; “Preparation and Proper-
ties of Crosslinked Hybrid Proton Exchange Membrane Based on
Sulfonated Poly(arylene Ether Nitrile) with Improved Selectivity
for Fuel Cell Application,” Ionics, 23, 671–679 (2017)
Matsumoto, K., T. Ishizuka, K. T. Harada and H. Matsuoka; “Association
Behavior of Fluorine-Containing and Non-Fluorine-Containing
Methacrylate-Based Amphiphilic Diblock Copolymer in Aqueous
Media,” Langmuir, 20, 7270–7282 (2004)
Mineart, K. P., X. Jiang, H. Jinnai, A. Takahara and R. J. Spontak; “Mor-
phological Investigation of Midblock-Sulfonated Block Ionomers
Prepared from Solvents Differing in Polarity,” Macromol. Rapid
Commun., 36, 432–438 (2015)
Ozmaian, M. and R. Naghdabadi; “Modeling and Simulation of the
Water Gradient within a Nafion Membrane,” Phys. Chem. Chem.
Phys., 16, 3173–3186 (2014)
Pai, T. S. C., C. Barner-Kowollik, T. P. Davis and M. H. Stenzel;
“Synthesis of Amphiphilic Block Copolymers Based on Poly-
(dimethylsiloxane) via Fragmentation Chain Transfer (RAFT)
Polymerization,” Polymer (Guildf.), 45, 4383–4389 (2004)
Park, C. H., C. H. Lee, M. D. Guiver and Y. M. Lee; “Sulfonated Hydro-
carbon Membranes for Medium-Temperature and Low-Humidity
Proton Exchange Membrane Fuel Cells (PEMFCs),” Prog. Polym.
Sci., 36, 1443–1498 (2011)
Ran, J., L. Wu, Y. B. He, Zh. J. Yang, Y. M. Wang, C. X. Jiang, L. Ge, E.
Bakangura and T. W. Xu; “Ion Exchange Membranes: New Devel-
opments and Applications,” J. Membr. Sci., 522, 267–291 (2017)
Roy, A., X. Yu, S. Dunn and J. E. McGrath; “Influence of Microstruc-
ture and Chemical Composition on Proton Exchange Membrane
Properties of Sulfonated–Fluorinated, Hydrophilic–Hydrophobic
Multiblock Copolymers,” J. Membr. Sci., 327, 118–124 (2009)
Seh, Z. W., J. Kibsgaard, C. F. Dickens, I. Chorkendorff, J. K. Nør-
skov and T. F. Jaramillo; “Combining Theory and Experiment
in Electrocatalysis: Insights Into Materials Design,” Science, 355,
eaad4998 (2017)
Shin, D. W., S. Y. Lee, C. H. Lee, K. S. Lee, C. H. Park, J. E. McGrath, M.
Zhang, R. B. Moore, M. D. Lingwood, L. A. Madsen, Y. T. Kim, I.
Hwang and Y. M. Lee; “Sulfonated Poly(arylene Sulfide Sulfone Ni-
trile) Multiblock Copolymers with Ordered Morphology for Pro-
ton Exchange Membranes,” Macromolecules, 46, 7797–7804 (2013)
Strathmann, H., A. Grabowski and G. Eigenberger; “Ionexchange Mem-
branes in the Chemical Process Industry,” Ind. Eng. Chem. Res., 52,
10364–10379 (2013)
Takamuku, S. and P. Jannasch; “Multiblock Copolymers with Highly
Sulfonated Blocks Containing Di- and Tetrasulfonated Arylene
Sulfone Segments for Proton Exchange Membrane Fuel Cell Ap-
plications,” Adv. Energy Mater., 2, 129–140 (2012)
Vol. 53  No. 11  2020
Ting, S. R. S., M. Gregory and M. H. Stenzel; “Polygalactose Containing
Nanocages: The RAFT Process for the Synthesis of Hollow Sugar
Balls,” Biomacromolecules, 10, 342–352 (2009)
Varcoe, J. R., P. Atanassov, D. R. Dekel, A. M. Herring, M. A. Hickner,
P. A. Kohl, A. R. Kucernak, W. E. Mustain, K. Nijmeijer, K. Scott,
T. W. Xu and L. Zhuang; “Anionexchange Membranes in Elec-
trochemical Energy Systems,” Energy Environ. Sci., 7, 3135–3191
(2014)
Verma, M. L., M. Minakshi and N. K. Singh; “Structural and Electro-
chemical Properties of Nanocomposite Polymer Electrolyte for
Electrochemical Devices,” Ind. Eng. Chem. Res., 53, 14993–15001
(2014)
Vincent, I. and D. Bessarabov; “Low Cost Hydrogen Production by
Anion Exchange Membrane Electrolysis: A Review,” Renew.
Sustain. Energy Rev., 81, 1690–1704 (2018)
Wang, Y. Y., F. Fan, A. Agapov, T. Saito, J. Yang, X. Yu, K. L. Hong, J.
Mays and A. P. Sokolov; “Examination of the Fundamental Rela-
tion between Ionic Transport and Segmental Relaxation in Poly-
mer Electrolytes,” Polymer (Guildf.), 55, 4067–4076 (2014)
Wang, C., B. Mo, Z. He, Q. Shao, D. Pan, E. Wujick, J. Guo, X. Xie, X.
Xie and Z. Guo; “Crosslinked Norbornene Copolymer Anion
Exchange Membrane for Fuel Cells,” J. Membr. Sci., 556, 118–125
(2018)
Wang, L., Z. Liu, Y. Liu and L. Wang; “Crosslinked Polybenzimidazole
Containing Branching Structure with No Sacrifice of Effective
N–H Sites: Towards High-Performance High-Temperature Proton
Exchange Membranes for Fuel Cells,” J. Membr. Sci., 583, 110–117
(2019)
Woeste, G., W. H. Meyer and G. Wegner; “Copolymers of Ethyl p-
Vinylbenzenesulfonate for the Preparation of Polyelectrolytes of
Reproducible Ion Content,” Makromol. Chem., 194, 1237–1248
(1993)
Xiao, R., J. K. Guo, D. L. Safranski and T. D. Nguyen; “Solvent-Driven
Temperature Memory and Multiple Shape Memory Effects,” Soft
Matter, 11, 3977–3985 (2015)
Zawodzinski, T. A. Jr., C. Derouin, S. Radzinski, R. J. Sherman, V. T.
Smith, T. E. Springer and S. Gottesfeld; “Water Uptake by and
Transport Through Nation 117 Membranes,” J. Electrochem. Soc., 4,
1041–1047 (1993)
Zhao, S. X., J. J. Zhang and Y. X. Wang; “Electro-Casting of Proton
Exchange Membranes from a Heterogeneous Solution,” J. Power
Sources, 242, 23–27 (2013)
Zhao, Y. X., Y. Q. Fu, B. Hu and C. L. Lü; “Quaternized Graphene Oxide
Modified Ionic Cross-Linked Sulfonated Polymer Electrolyte
Composite Proton Exchange membranes with Enhanced Proper-
ties,” Solid State Ion., 294, 43–53 (2016)
Zheng, Y. W., U. Ash, R. P. Pandey, A. G. Ozioko, J. Ponce-Gonzalez, M.
Handl, T. Weissbach, J. R. Varcoe, S. Holdcroft, M. W. Liberatore,
R. Hiesgen and D. R. Dekel; “Water Uptake Study of Anion Ex-
change Membranes,” Macromolecules, 51, 3264–3278 (2018)
Ziv, N. and D. R. Dekel; “A Practical Method for Measuring the True
Hydroxide Conductivity of Anion Exchange Membranes,” Electro-
chem. Commun., 88, 109–113 (2018)
Zlotorowicz, A., R. V. Strand, O. S. Burheim, Ø. Wilhelmsen and S. Kjel-
strup; “The Permselectivity and Water Transference Number of Ion
Exchange Membranes in Reverse Electrodialysis,” J. Membr. Sci.,
523, 402–408 (2017)
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