Facile synthesis of poly (arylene ether ketone)s

containing flexible sulfoalkyl groups with enhanced

oxidative stability for DMFCs
Group 2
Member 01
Nabilah Sayidatu S
1187040040

Group 02
Novi Sulistiawati
1187040044

Nurul Fatihah Hasan

03 1187040049

Rizki Nur Alam

04 1187040060

Silmi Rahma Amelia

05 1187040070
 INTODUCTION
• As one of the most important type of fuel cells, direct methanol fuel cell (DMFC) has attracted significant
attention because of its inherent merits, such as high energy efficiency, low emission, convenient refueling
and portability [1-3]. The proton exchange membrane (PEM), as the vital component of DMFC, serves as a
physical separator between the fuel and the oxidant as well as an electrical insulator, and more importantly
a proton conductor. To date, the most widely investigated and commercialized PEMs are perfluorosulfonic
acid (PFSA) polymeric membranes.

• Among all these alternative polymers, SPAEs are considered to be the potential alternatives to Nafion
membrane in DMFCs due to their low methanol permeability, good thermal and mechanical stabilities,
flexible structural design and low fabrication cost.

• In this study, novel side-chain-type SPAEs with clustered sulfoalkyl pendants were prepared via a facile
procedure involving polymerization, bromomethylation and nucleophilic substitution. Tetrabenzylmethyl-
containing poly(arylene ether ketone) (TMPAEK) was first synthesized from 3.3’,5,5’-tetramethyl-4,4’-
bisphenol (TMBP), and then bromomethylated via a free-radical substitution reaction which was triggered
by benzoyl peroxide (BPO) and N-bromosuccinimide (NBS)
 Material
1 TMBP (98%) 6 potassium carbonate

2 4,4’-difluorobenzophenone (DFBP, 98%) 7 Toluene

3 NBS (98%) 8 dimethylsulfoxide (DMSO)

4 MTS (98%) 9 N-methyl-2-pyrrolidone (NMP)

5 BPO (>98%)
Experimental, Result, and
Discussion
Scheme 1 - Synthesis of TMPAEK, BrPAEK and MTSPAEK.
Preparation and bromomethylation of
poly(arylene ether ketone)

After washing with distilled water and

ethanol, the resulted precipitate was driedin
a vacuum oven at 100 oC.

Then the system was heated to 180 oC and maintained for another
6 h, followed by pouring the viscous mixture into distilled water with
manually stirring to precipitate raw product

The mixture was stirred and kept at 140 oC for 2 h to

remove the generated water

24.2 g TMBP (0.1 mol), 21.8 g DFBP (0.1 mol), 13.8 g potassium carbonate (0.1 mol), 250 mL NMP
and 70 mL toluene were added to a three-necked flask under N 2 protection.

TMPAEK was prepered

 The bromomethylation procedure

The obtained polymer termed as BrPAEK was placed in a vacuum

oven at 60 oC for 24 h and then collected.

the product was precipitated by pouring the mixture into 500 mL acetone
and purified by washing with acetone several times

After TMPAEK was completely dissolved, 8.4 g NBS and 1.2 g BPO were added into the flask and
the mixture was maintained at 60 oC for 12 h under nitrogen atmosphere.

10.0 g TMPAEK and 100 mL chloroform were introduced into a 250 mL

threenecked flask
 Grafting of MTS onto BrPAEK

The product termed as MTSPAEK was precipitated and purified in

ethanol.

The mixture was stirred and kept at 140 oC for 2 h to

remove the generated water

the solution of BrPAEK in NMP was added to the flask with a dropping funnel and the mixture was
kept at 80 oC for another 12 h to complete the reaction

1.9 g MTS, 0.9 g K2CO3 and 20 NMP were dissolved in a flask by stirring under
nitrogen protection
Preparation of MTSPAEK membranes

The membranes with the thicknesses of 60-

80 μm were dried in vacuum at 60 oC for 24
h.

the acid-type membranes were washed with deionized water several

times and soaked into deionized water for 2 days to remove any
excess acid

. The membranes were acidified in 2M HCl for 24 h at 60 oC to convert Na+

into H+ completely

. After solvent evaporation at 60 oC for 24 h, the glass plates were immersed into deionized water to
peel off the membranes

DMSO solution casted with the concentration of 10 wt% onto clean glass
plates
 MEASUREMENT

 
…………… (1)
 Strucutral Characterization

Figure 1. The 1H NMR spectra of BrPAEK (a) and MTSPAEK (b)

Thermal and Oxidative Stability

Figure 2. The TGA curves of MTSPAEK membranes under nitrogen

 Mechanical Property

Figure 3. The stress-stain curves of MTSPAEK membranes

Scheme 2 – Proposed antioxidant process for MTSPAEK containing thioether groups
Ionic exchange capacity (IEC) :
• Table 3 show that the IECb value measured by titration increased from 1.89 to 2. 57 mequiv.g -1 as the number of pendant
sulfoalkyl groups increases.
• the measured IEC value is close to the theoretical value determined by NMR. This small difference may be due to imperfect
proton exchange in the membrane.
Water Uptake (WU) and Swelling Ratio (SR) :
• The MTSPAEK-2.10 membrane showed the highest WU value of 87% at 80 C, higher than the Nafion recast membrane (69%)
as shown in Table 3.
• From fig 4 & 5 the values ​of WU and SR increase with increasing temperature and IEC.

• However, the SR of the MTSPAEK-2.10 membrane was only 29% at 80 C, which is close to Nafion recast membrane (30%).

• SR MTSPAEK-2.10 was below 15% at 30 C, lower than the recast Nafion membrane (23%), although the WU MTSPAEK and
recast Nafion were almost the same at the same temperature.

• These results indicate that MTSPAEK can absorb more water but resist excessive swelling.
Proton Conductivity

Methanol permeability and relative selectivity

 
Rs =
Proton Conductivity and Membrane Micro Structure

• The proton conductivity of the MTSPAEK membrane is

measured in the range 30 - 80 ° C in the fully hydrated state.
• From Fig. 6 all MTSPAEK membranes show a trend of
increasing proton conductivity with increasing temperature,
since high temperatures usually increase membrane hydration
and water diffusion. MTSPAEK membranes show an
increasing trend with increasing IEC.
• The MTSPAEK-2.10 membrane had the highest proton
conductivity of 0.181 S cm-1 at 80 C, which was also higher
than that of the recast Nafion (0.14 S cm-1) tested under the
same conditions.
Proton Conductivity and Membrane Micro Structure

• From Fig. 7 the dark areas in the phase image are assigned to the
soft part of the hydrophilic sulfonic acid groups which contain
water and the dark areas tend to be more expansive and
interconnected to form a larger hydrophilic ionic domain with an
increasing IEC value.
• whereas the bright areas correspond to the hard hydrophobic
domains of the aromatic polymer backbone.
• MTSPAEK-2.10 membrane which has the best hydrophilic ionic
domain connectivity shows the highest proton conductivity. Thus,
the proton conductivity of the MTSPAEK membrane closely
matches the microstructure of the membrane.
 Methanol permeability and relative selectivity

• The methanol permeability of MTSPAEK and Nafion rekast membranes was measured at 30 ° C under the same conditions for
comparison (Table 3). Methanol permeability ranged from 2.37 x 10-7 to 7.80 x 10-7 cm2 s-1 and showed an increasing trend
with the increase in IEC, as well as WU and SR.
• MTSPAEK-2.10 showed the highest methanol permeability, namely 7.80 x 10-7 cm2 s-1, which is still much lower than the
recast Nafion (21.87 x 10-7 cm2 s-1).
• MTSPAEK membranes showed a slight decrease in relative selectivity with increasing IEC. The results showed that the
MTSPAEK membrane has the potential to overcome problems caused by the high methanol permeability of PEMs in DMFCs.
Single cell performance
Single cell performance

• MTSPAEK-2.10 membrane was chosen to be fabricated into

MEA to evaluate its performance in single DMFC cells
because it has the highest proton conductivity. Fig. 8 shows
the polarization curves and power density of MTSPAEK-2.10
at different temperatures.
• The maximum power density and current density increase
with increasing temperature because proton conductivity
increases at high temperatures. MTSPAEK-2.10 shows a
maximum power density of 70 mW cm-2 at a current
density of 320 mA cm-2 at a temperature of 80 C.
• These results suggest the MTSPAEK membrane has great
potential as a promising alternative to Nafion for DMFC
applications.
 CONCLUSION

Poly(arylene ether ketone)s containing clustered

pendant sulfoalkyl groups were successfully
synthesized by a facile grafting reaction between
mercapto groups and benzyl bromide groups. The
resulted membranes exhibited excellent thermal and
mechanical stabilities. In these results suggest
MTSPAEK membranes are of great potential as the
promising alternative to Nafion for DMFC
applications. In addition, the grafting reaction
between mercapto groups and aryl halides groups
may be a feasible strategy to prepare polyelectrolyte
materials with enhanced oxidative stability.
THANK YOU
 Table 1. The degree of sulfonic acid grafting, inherent viscosity, thermal and
oxidative stability of MTSPAEK membranes.

Sample DBr Dg (%) [η] (dL g-1) Tg (℃) Td5% (℃) RW (%) τ (min)

MTSPAEK-1.53 1.53 80.1 0.80 196 264 94.9 94

MTSPAEK-1.77 1.77 79.2 0.82 200 263 96.6 116

MTSPAEK-1.92 1.92 78.7 0.87 201 261 97.8 164

MTSPAEK-2.10 2.10 78.3 0.91 208 259 98.0 228