Synthesis and Characterization of Polyimide-Polysiloxane

Segmented Copolymers for Fuel Cell Applications

LIJUN ZOU, MITCHELL ANTHAMATTEN
Department of Chemical Engineering, University of Rochester, 206 Gavett Hall, Rochester, New York 14627

Received 3 November 2006; accepted 17 March 2007

DOI: 10.1002/pola.22125
Published online in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: Sulfonated polyimides exhibit high strength, good film-forming ability,

chemical resistance, and, in their hydrated state, relatively high proton conductivity.
Here we report the one-pot synthesis of sulfonated polyimide-polysiloxane segmented
copolymers through the reaction of a dianhydride with a mixture of three diamines: a
nonionic aromatic diamine (4,40 -oxydianiline), a sulfonated diamine (4,40 -diamino-2,20 -
biphenyldisulfonic acid), and a telechelic diamino polysiloxane. Copolymer com-
positions were evaluated using 1H NMR and size-exclusion chromatography. The
presence of ion-containing diamines in the reaction mixture inhibited stoichiometric
incorporation of hydrophobic siloxane segments. Siloxane segments were found to
lower the thermal stability of the polyimide host. Copolymers with and without silox-
ane segments were cast into free-standing films. Equilibrium water sorption studies
of cast films show that, for the compositions studied here, the presence of siloxane
segments does not interfere with water swelling, suggesting that a microphase-segre-
gated morphology may exist. TEM and SAXS analyses show evidence of phase-segre-
gation in sulfonated polyimides and reveal that siloxane segments strongly affect
ionic clustering. However, proton conductivity only changes slightly when polysilox-
ane segments are incorporated. V C 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym

Chem 45: 3747–3758, 2007

Keywords: ionomers; morphology; polyimides; polysiloxanes

INTRODUCTION suffer from several drawbacks: (1) they are ex-

The role of the proton exchange membrane
(PEM) in a fuel cell is to separate anode and
cathode reactive gases while serving as a con-
duit for protons to pass between electrodes. The
main qualities of PEM materials include high
proton conductivity, good mechanical and ther-
mal stability, low gas permeability, and low elec-
tro-osmotic drag.1–7 The state-of-the-art PEM
contains perfluorosulfonic acid (PFSA) polymers
such as Nafion1. However, PFSA membranes
Correspondence to: M. Anthamatten (E-mail: anthamatten@
che.rochester.edu)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 45, 3747–3758 (2007)
V
C 2007 Wiley Periodicals, Inc.
pensive, (2) membrane gas crossover leads to
inefficiencies, (3) Nafion faces environmental
incompatibility issues, and (4) they are unsuit-
able for high-temperature applications. PFSA
polymers dry out at high operating tempera-
tures, and due to their low glass transition tem-
perature (
110 8C) their mechanical properties
deteriorate.
For the development of new generation of
polymer membranes for PEMFCs, extensive
materials have been studied, for example, fluo-
rine-containing polybenzimidazole,8 Poly(arylene
ether sulfone),9 vinylidene fluoride based terpol-
ymers,10 and crosslinkable sulfonated poly(ether
ether ketone)s.11 Among them, sulfonated poly-
imides (SPIs) have been one of the most promis-
3747
3748 ZOU AND ANTHAMATTEN
ing materials, and they have been developed as
an alternative to Nafion to leverage polyimide’s
good mechanical properties and excellent ther-
mal and oxidative stability. Much has been writ-
ten about the synthesis of SPIs using various
sulfonated diamines.7,12-19 In general, SPIs ex-
hibit high proton conductivity, good mechanical
strength and water-swelling behavior, although
they do suffer from hydrolytic degradation.14,20
However, consideration and design of polyimide
molecular structure, and careful selection and
positioning of sulfonate groups can significantly
improve hydrolytic stability.21–23
Despite the intense research in the area of sul-
fonated rigid-rod polymers, fundamental studies
of morphology and ion-ordering are scarce. Kreuer
et al. have conducted systematic studies on rigid-
rod sulfonated polyetherketones (SPEEKK),24
and they propose that weaker hydrophilic/hydro-
phobic interactions result in a very different
microstructure (compared to Nafion). Intercon-
nected hydrophilic channels are believed to be
narrower, more highly branched, and contain
many more dead-end channels than Nafion. This
idea, combined with the view that sulfonate
groups are more compatible with polymer groups
present on rigid-rod chains (like SPEEK or poly-
imide), one would expect a greater degree of mo-
lecular-level mixing to occur in rigid-rod derived
ionomers compared to a fluorocarbon phase.
Indeed, for SPIs, small angle X-ray scattering
experiments typically do not show any evidence of
nanoscale segregation.25 The absence of Bragg
scattering peaks is attributed to the low flexibility
of the aromatic hydrocarbon electrolytes as well
as the less pronounced differences between the
hydrophilic and hydrophobic molecular parts. On
the other hand, phase-segregated morphologies
are observed if flexible anhydride or diamine
building blocks are used,26 or if sulfonic acid
groups are attached to rigid-rod polymers using a
flexible spacer.17
Here, in an effort to influence the ordering
and distribution of ionic clusters in rigid-rod ion-
omers, we report on the synthesis and charac-
terization of a new class of SPI copolymers that
contain polysiloxane segments. Polysiloxanes
are incompatible with polyimides, and micro-
phase-segregation has been observed in similar
block copolymers.27–29 We chose to incorporate
incompatible siloxane segments to promote
structure formation on the same length scale as
ionic cluster ordering and to stabilize well-
dispersed morphologies. In principle, microphase
segregation of incompatible siloxane domains
could lead to the formation of ion-rich channels
and improved proton conduction. In addition,
polysiloxanes can impart several beneficial prop-
erties such as enhanced solubility, thermal and
UV stability, resistance to degradation in
aggressive oxygen environments, and enhanced
adhesive properties; though, it is realized that
low gas permeability may be compromised, lead-
ing to fuel crossover. The goal of this work is
to develop a method of synthesizing sulfonated
polyimide-polysiloxane (SPI-PSX) segmented co-
polymers and study their structure-property
relationships. In the following, we describe a
one-pot synthesis of SPI-PSX segmented copoly-
mers that enables tuning of both the ionic con-
tent and the siloxane content. Small angle X-ray
scattering and transmission electron microscopy
are used to study the resulting morphologies.
EXPERIMENTAL
Materials
4,40 -oxydianiline (ODA) (99þ%), 1,4,5,8-naphtha-
lenetetracarboxylic dianhydride (NTDA) (99%)
and Toluene (99%) were purchased from Aldrich;
NMP (99.5%, anhydrous), triethylamine (TEA),
benzoic acid (99%), and 4,40 -diamino-2,20 -biphe-
nyldisulfonic acid (BDSA) (97%) from VWR; hy-
drochloric acid (HCl, 36.9%), sodium chloride
(NaCl, 100%) from J. T. Baker; dimethyl sulfox-
ide (DMSO) from EMD Chemicals Inc., and ami-
nopropyl-terminated polydimethylsiloxane (PSX,
Mn ¼ 4200 g/mol and 2335 g/mol, measured
using vapor phase osmometry in our lab, cali-
brated with PS in toluene) from UCT and
Sigma-Aldrich. All materials were used without
further purification except NTDA, which was
vacuum-dried at 170 8C for 12 h, and BDSA,
which was vacuum-dried at 90 8C for 12 h,
before use.
Synthesis
SPI-PSX Segmented Copolymers
In a typical synthesis, BDSA, ODA and NMP
were added to a completely dried 100 mL 3-neck
flask equipped with a Dean-Stark trap and a
condenser under nitrogen purge. In addition,
TEA was added to improve the solubility of
BDSA and benzoic acid functioned as cata-
lyst.30–32 After all reagents were dissolved, PSX
Journal of Polymer Science: Part A: Polymer Chemistry
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 SULFONATED POLYIMIDE-POLYSILOXANE COPOLYMER 3749

Scheme 1. One-pot synthesis leading to SPI-PSX segmented copolymers.

in toluene solution was added to the mixture, Characterization

and NTDA and benzoic acid were added into the
Free-standing films (
30 lm) were studied
solution. The final volume ratio of NMP to tolu-
using a Nicolet 20SXC infrared spectrometer. 1H
ene is 4:1. The mixture was stirred at room tem-
NMR spectra were recorded on a Bruker 400
perature overnight and then heated to 80 8C for
MHz NMR spectrometer with DMSO-d6 as a sol-
4 h and to 180 8C for 20 h (Scheme 1). Collected
vent. Thermogravimetry was performed with a
water was removed from the Dean-Stark trap
simultaneous DSC-TGA instrument (SDT600) at
with toluene. The warm solution containing
a heating rate of 10 8C/min under nitrogen.
product was poured into 300 mL acetone, and
Molecular weights were measured via gel per-
the resulting precipitate was filtered, washed
meation chromatography (GPC) (Viscotek, TDA
with acetone and THF successively, and dried in
Model 301, Triple Detector Array) using NMP
vacuum oven at 80 8C for 15 h.
with LiBr (0.02 M) as the mobile phase at 60 8C
Unsulfonated polyimides (PIs) and sulfonated
and flow rate of 0.8 mL/min. Prior to injection,
polyimides (SPIs) were also synthesized as con-
samples were filtered with stainless steel sup-
trol samples. This procedure is similar to that
ported PTFE porous membranes (0.2 lm) (Pall
described above, but without addition of BDSA
Corp.). The injection volume was 100 lL of stock
and/or PSX, using NMP as the only solvent.
solution (
2 mg/mL) and calibration was per-
formed with polystyrene standards. For mor-
phology observations, protonated film samples
Film Casting and Ion Exchange
were ion-exchanged with silver cations by
The SPI-PSX powder product was dissolved in immersion overnight in a 0.1 M AgNO3 aqueous
DMSO or NMP (5 wt %) and then cast into films solution followed by DI water rinsing and room
on glass or PDMS surfaces. After drying at temperature drying. Stained samples were then
120 8C for 12 h, the as-cast films were soaked in embedded in an epoxy resin, sectioned to a
methanol at 60 8C for 4 h and then were soaked 100 nm thickness using a microtome (MT 6000,
overnight at room temperature in 1.0 M HCl. RMC), and floated onto copper grids. Images
The protonated films were washed thoroughly were taken on JEOL-2000EX transmission elec-
with deionized (DI) water and then vacuum tron microscope (TEM) with an accelerating
dried at 150 8C for 24 h. voltage of 200 kV.
Journal of Polymer Science: Part A: Polymer Chemistry
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3750 ZOU AND ANTHAMATTEN
Figure 1. Flow diagram for dynamic water sorption
apparatus.
Small-angle X-ray scattering (SAXS) data
were acquired using the D1 SAXS/GISAXS
beamline at the Cornell High-Energy Synchro-
tron Source (CHESS) (Ithaca, NY). Data were
background-subtracted and integrated using
the Fit 2d program.33 The scattering vector is
defined as q ¼ 2p sin h/k, where h is the scatter-
ing angle and k is the incident wavelength of
1.197 Å. All X-ray experiments were performed at
ambient humidity conditions on film samples
that were ion-exchanged with Cesium for con-
trast.
Water vapor sorption isotherms under differ-
ent relative humidity (RH) were acquired using
a Cahn-2000 environmental electro-balance (61
lg) that was adapted to control humidity around
the sample. The flow diagram for the apparatus
is shown in Figure 1. Dry nitrogen was fed to
two mass flow controllers (McMillan 80-3, 0–50
mL/min) prior to entering the sample exposure
chamber. One of these gas streams was sent
through a gas bubbler, and the other was sent
directly to the exposure chamber. The flow rates
of each of these streams was controlled using a
feedback signal from a humidity sensor (HIH-
3610) installed next to the sample. The RH sen-
sor was calibrated to standard salt solutions,
and the apparatus described can control humid-
ity between 5 and 80% with an accuracy of
about 61%. Samples (5–25 mg films) were sus-
pended in a hang-down stirrup that was con-
nected to the microbalance. The microbalance
was also purged with dry nitrogen. Time-
resolved data (mass, humidity, and temperature)
were continuously logged (Agilent 34970A data-
logger).
Ion exchange capacities (IEC) were measured
by soaking films (
50 mg) overnight at room
temperature in 1 M HCl to ensure protonation
of all sulfonic acid groups. After soaking, films
were thoroughly washed with DI water several
times and then were ion-exchanged in 100 mL
0.1 M NaCl by soaking overnight. The pH value
of the proton-exchanged NaCl solution was
measured using a pH meter (Orion 710A plus)
and the IEC [meq/g] was determined from
10pH 3 VNaCl
IEC ¼ ð1Þ
m0
where VNaCl [L] is the volume of NaCl solution,
and m0 [kg] is the original dry mass of the poly-
mer film.
The proton conductivity of the membranes
under different relative humidity was deter-
mined at 80 8C with a 4-point probe fuel cell
test and impedance analyzer (BekkTech) over
the frequency range of 1 Hz–10 KHz. Nitrogen
feed gas was used at flow rate of 500 cm3/min.
The resistance R of the membranes was taken
as the lowest frequency that produced a near-
zero imaginary response. The conductivity of the
membranes was calculated from the measured
resistance and the geometry of the cell by using
the following equation:
0:425½cm
r½S=cm ¼ ð2Þ
R½X 3 W½cm 3 T½cm
where 0.425 [cm] is the fixed distance between
two cell electrodes, and W and T are the width
and thickness of the sample membrane, respec-
tively.
RESULTS AND DISCUSSION
The structure and properties of sulfonated poly-
imides depend on the mode and order of mono-
mer addition.34,35 In a typical synthesis, PSX
was first mixed with the other diamine mono-
mers using NMP and toluene as cosolvents, and
then the solid anhydride was added to the solu-
tion. This method was found to maintain better
solubility during the addition steps. Homo-
geneous solutions were only obtained after
increasing the temperature above 80 8C. As the
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 SULFONATED POLYIMIDE-POLYSILOXANE COPOLYMER 3751

Table 1. Feed Composition, Solubility, Molecular Weight, and Ionic-Content Characteristics, of Synthesized
Polyimides

Overall Feed Measured

Composition Compositionc Calculated
Compositiond
PSX BDSA WU Mn IEC PSX BDSA BDSA
Samplea (wt %) (wt %) Solubilityb (%) (g/mol) (meq/g) (wt %) (wt %) (wt %)

N-O 0 0 3 – – – – – –
N-OB 0 31.9 H 54.8 16,300 1.57 0.0 33.3 33.3
N-OBP-1 40.0 5.0 3 – – – – – –
N-OBP-2 10.0 14.0 o – – – 12.0 25.5 –
N-OBP-3 30.0 14.0 o – – – 7.4 28.9 –
N-OBP-4 50.7 14.0 H 24.6 10,300 1.28 30.8 23.1 27.2
N-OBP-5 10.0 30.0 H 48.1 16,900 1.48 0.8 38.4 31.5
N-OBP-6 10.0 30.0 H 50.0 14,400 1.71 0.9 37.7 36.4
N-PþN-OB 10.0 30.0 H 54.0 13,500 1.66 1.4 35.6 35.3
N-OBP-7 20.0 30.0 H 69.9 9,800 1.96 1.3 41.4 41.7
N-OBP-9e 30.0 30.0 H 82.1 18,100 2.15 3.2 48.0 45.7
N-OBP-10e 30.0 22.0 H 42.5 6,600 1.47 3.2 33.7 31.3
N-PþOBe 30.0 22.0 H 55.1 8,000 1.67 3.7 34.2 35.5
a
N: NTDA; O: ODA; B: BDSA; P: PSX.
b
Solubility tested in NMP with 5 wt % concentration of each sample. 3: insoluble; o: partly soluble; H: soluble.
c
Determined by NMR integration of acidified polymers.
d
Determined by IEC measurement of acidified polymers.
e
Samples synthesized using PSX having a MW of 2,335 g/mol. All the others samples involved PSX with MW of 4,200 g/mol.

reaction proceeded, the solution became darker,
and the viscosity steadily increased.
All synthesized sulfonated polyimide copoly-
mers are listed in Table 1. Product polymers
were soluble in aprotic solvents including NMP
and m-cresol, and most polymers could be cast
onto flat glass surfaces. Free-standing films
were obtained after soaking cast films into DI
water for 2–5 h. Upon soaking, most samples
spontaneously delaminated or could be easily
peeled from their glass substrates. However,
samples with siloxane contents greater than 3%
adhered strongly to glass surfaces, and could
not be peeled off. These samples were cast, and
easily separated from, flexible polymer sub-
strates.
Figure 2 shows the FT-IR spectrum of N-
OBP-4, in film form (
30 lm). The absorption
observed at 1792 cm1 is likely due to anhydride
end-groups, rather than unreacted monomer

Figure 2. FT-IR spectrum of N-OBP-4. Peaks attributed to siloxane block are

underlined.
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3752 ZOU AND ANTHAMATTEN

Table 2. FT-IR Assignments for Sulfonated Polyimide-Polysiloxane Copolymers

Peak
Frequency [cm1] Vibrational Mode Shape

3437 HO stretch from absorbed H2O Broad

2965 CH stretch of methyl group within PSX Sharp
1792 Anhydride carbonyl group Sharp
1717 imide carbonyl group (symmetric stretch) Sharp
1676 imide carbonyl group (asymmetric stretch) Sharp
1330 CN C imide ring mode Sharp
1198–1263 Symmetric and asymmetric S¼ ¼O stretch Broad
in sulfonic acid groups
1020–1090 O
Si Si and Si O stretch Broad
704–881 C stretch
Si Medium broad

which should be completely removed during
washing and film-casting steps. This signal dis-
appears upon overnight exposure to air, suggest-
ing facile hydrolysis of anhydride end-groups.
The symmetric and asymmetric stretch of imide
carbonyl groups were observed at 1717 cm1
and 1676 cm1. The C H stretch of methyl
group associated with PSX was observed at
2965 cm1, and this absorption qualitatively
confirms that siloxane segments were incorpo-
rated into the synthesized copolymers. The peak
at 1020–1090 cm1 was assigned to SiOSi
and SiO stretch in the siloxane backbone.
However, this signal overlaps with much weaker
absorption from sulfonic acid groups appearing
in the same region. All samples were repeatedly
washed with THF to remove any unreacted
polysiloxanes. A complete list of vibration modes
of these and other peaks is provided in Table 2.
Peak assignments are based on those made by
others.14,36-38
The 1H NMR spectrum of a typical SPI-PSX
copolymer is shown in Figure 3. Proton peaks
from methyl groups of PSX are present around
d ¼ 0, confirming the incorporation of PSX in
the polymer. If one assumes that polymer chains
consist of an equal number of anhydride and
diamine repeat units, then the composition of

1
Figure 3. H NMR spectrum of N-OBP-4 with triethyl ammonium counter-ions.
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola

synthesized copolymers can be determined
directly from the 1H NMR spectra. To do this,
the integrated 1H NMR intensities of NTDA
aryl protons adjacent to ODA, BDSA, and
PSX units were calculated and compared. For
example, the integrated NMR signal for NTDA
aryl protons that are adjacent to ODA units
INTDA-ODA is given by
4
INTDA-ODA ¼ ðIb þ Ic Þ
8 NTDA was first reacted with PSX (at a molar
where Ib and Ic are the integrated NMR signal
for ODA aryl protons shown in Figure 3 (d
¼ 7.61 and d ¼ 7.35), and the ratio 4/8 accounts
for the fact that there are 4 NTDA aryl protons
per 8 ODA aryl protons. Note that Ic can be
obtained from the NMR peak at d ¼ 7.35
because Ic ¼ Ib. A similar procedure is repeated
for PSX to obtain INTDA-PSX, given by
Ij 3 4
INTDA-PSX ¼
6 3 54
where Ij is the integrated NMR signal for PSX
methyl protons shown in Figure 3 (d ¼ 0), and
the ratio 4/(6 3 54) accounts for the fact that
there are 4 NTDA aryl protons per 324 PSX
methyl protons for PSX of molecular weight Mn
¼ 4200 g/mol. A similar procedure is repeated
for BDSA to obtain INTDA-BDSA. Therefore, the
ratio INTDA-ODA:INTDA-BDSA:INTDA-PSX is equal to
the polymer’s molar composition x:y:z.
As shown in Table 1, measured compositions
from 1H NMR are quite different from feed com-
positions for many of the copolymers. This is
especially true for the PSX content—there were
only a few samples (e.g., N-OBP-2 and N-OBP-
4) that showed a high level of PSX content
following synthesis and washing. In all other
samples, the feed composition is typically sev-
eral times greater than the measured composi-
tion. Several experiments were conducted to
explain this difference. One possible explanation
is that the high reaction temperature (180 8C)
causes the thermal degradation. To rule out this
possibility, N-OBP-6 was synthesized using the
same feed composition as N-OBP-5 but with a
lower reaction temperature (165 8C). Both N-
OBP-5 and N-OBP-6 had similar measured si-
loxane compositions (0.8 and 0.9 wt %, respec-
tively), suggesting that thermal degradation
does not lead to lower siloxane content. To test
whether the order of monomer addition affects
the content of PSX in the final product, we syn-
Journal of Polymer Science: Part A: Polymer Chemistry
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SULFONATED POLYIMIDE-POLYSILOXANE COPOLYMER 3753
thesized N-PþN-OB and N-PþOB, which have
the same feed composition as N-OBP-6 and N-
OBP-10 but monomers were added sequentially.
For N-PþN-OB the NTDA was first reacted
with PSX and, in a separate flask, NTDA was
reacted with ODA/BDSA. The two flasks were
stirred at room temperature for 2 h, and then
solutions were combined into a single flask. The
mixture was stirred and reacted as described in
ð3Þ the Synthesis section. For N-PþOB, excess
ratio 11.2:1.0) in one flask with a cosolvent of
NMP/toluene. After 1 h, a solution of BDSA and
ODA in NMP/toluene was added into the NTDA/
PSX, and the mixture was stirred and reacted
as described in the Synthesis section. As Table 1
indicates, the modified methods did not have
significant effect on the PSX content in the final
products. Another possible explanation for the
low PSX content in the final products is that the
siloxane monomers are too high in molecular
ð4Þ weight, and this limits their reactivity relative
to competing small molecule diamines. For N-
OBP-9, N-OBP-10, and N-PþOB, amino-termi-
nated siloxanes of lower molecular weight (Mn
¼ 2335 g/mol) were used instead of the control
siloxanes (Mn ¼ 4200 g/mol). These copolymers
made from low molecular weight siloxanes all
showed
3 wt % PSX content. It is possible that
the coupling reaction rate is more efficient for
lower molecular weight siloxane precursors; sim-
ilar effects have been reported in studies on
unsulfonated segmented poly(imide-siloxane)
copolymers.39 The factor that appears to have
the largest effect on the PSX content is the pres-
ence of charged BDSA groups. Table 1 shows
that products with lower BDSA feed composi-
tions consistently have higher PSX contents.
Ion exchange capacity (IEC) measurements
enable the BDSA content of synthesized SPIs to
be back-calculated. To do this, each BDSA mole-
cule was assumed to contain 1.62 ions-this num-
ber was obtained from careful analysis of the
control N-OB sample (NMR, GPC, IEC). Result-
ing values of BDSA content are shown in the
last column of Table 1, and they agree well with
compositions determined from NMR alone
(shown in the preceding column). This agree-
ment suggests that both NMR and IEC are reli-
able methods to determine the BDSA content of
synthesized materials.
IEC and water-uptake measurements were
only performed on products that exhibit good
film forming ability. Products with BDSA feed
3754 ZOU AND ANTHAMATTEN

composition greater than 22 wt % typically

showed better film forming ability. As expected,
IEC and water-uptake values both increase with
BDSA content. Products with high BDSA
content, for example N-OBP-7 and N-OBP-9,
readily swelled with water and showed the high-
est levels of water-uptake, although these films
were observed to be relatively brittle. Films
with lower BDSA feed composition, for example
N-OBP-1, tend to be insoluble and could not be
cast into films. Note that N-OBP-4, containing
the highest amount of siloxane (30.8 wt %),
exhibits somewhat less water uptake compared
to samples with similar ion content. This obser-
vation is likely due to the more hydrophobic
nature of the copolymer.
The water uptake values in Table 1 were
obtained by directly soaking solvent-cast, vac-
uum-dried films in deionized water. These mass-
uptake values will now be compared to films
exposed to water vapor at much lower activities.
Figure 4(a) shows an example of dynamic water
sorption data acquired at several different rela-
tive humidities for N-OB. In a typical experi-
ment, the mass of absorbed water plateaus to an
equilibrium value after about a half-hour. The
number of water molecules per mole of sulfonic Figure 4. (a) Dynamic water sorption (mass) of a 24
mg dry sample of N-OB (left ordinate) following step-
acid groups, k, was calculated for each level of
changes in relative humidity (right ordinate); (b) equi-
relative humidity according to
librium moles of water molecules present per mole of
SO3H at different relative humidity, determined
m  m0
k¼ ð5Þ from the equilibrium plateau in (a).
lw 3 m0 3 IEC

where m [kg] is the equilibrated mass, m0 [kg]
is the dry mass, lw [kg/mol] is the molar mass
of water, and IEC is the ion exchange capacity.
Equilibrium values of k are plotted against rela-
tive humidity for several synthesized samples in
Figure 4(b). All samples, including Nafion 117
(data collected from Ref. 40), showed similar
sorption characteristics over the humidity range
studied. At the highest humidity condition
(
95% RH), k
8–10 for all samples studied,
which is significantly less than that observed
in liquid WU experiments (k
11–21). This fea-
ture is commonly referred to as Schroeder’’s par-
adox and has been observed in other ionomer
materials.40,41
Among the samples shown in Figure 4(b), N-
OBP-5 and N-PþN-OB show higher levels of
water vapor sorption across the humidity range.
This is unexpected because these samples have
about the same ion-content as the reference
sample N-OB, and they contain hydrophobic
siloxane chains. Therefore, the data suggest
that the presence of siloxane segments does not
inhibit water vapor uptake in samples contain-
ing about 1% PSX. A similar comment can be
made at higher siloxane content. One would
expect N-OBP-4, containing
31 wt % siloxane
and the lowest ion content to exhibit very low
water uptake. Yet this sample shows nearly
identical water vapor sorption as (N-OB). To-
gether, these observations suggest siloxane-con-
taining materials organize into a morphology
where siloxane segments are excluded from
ionic-rich regions. The issue of phase-segrega-
tion and ion-aggregation will be discussed last.
Molecular weights were measured using GPC
for samples that could be dissolved in NMP,
and results are reported in Table 1. Samples
showed molecular weights from 6600 to 18,100
Daltons with polydispersities ranging from
2.0 to 3.0, and GPC traces showed no evidence
of ionic aggregation. Many of the SPIs with
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 SULFONATED POLYIMIDE-POLYSILOXANE COPOLYMER
Figure 5. TGA curves of (a) control samples and (b)
synthesized copolymers. Values in parenthesis denote
the measured BDSA content followed by the meas-
ured PSX content (wt %).
siloxane groups showed molecular weights
that were similar as those without siloxane
groups. The amino-terminated siloxane reagent
does not appear to act as a chain stopper during
synthesis.
Figure 5 shows the TGA mass-loss curves for
selected polymers. All samples were dried under
N2 purge at 180 8C for 10 h before the experi-
ment. The pure polyimide, N-O is stable up to
about 600 8C and shows a single-step mass loss.
Similarly, the polysiloxane diamine starting ma-
terial shows decomposition beginning around
350 8C. For all SPI copolymers studied, mass
loss occurs in two distinct steps. The first loss
occurs from 250 to 450 8C and is attributed to
loss of sulfonic acid side-groups (including trie-
thylamine counter ions), and, simultaneously to
decomposition of siloxane segments. N-OBP-4
contains 30.8 wt % siloxane and exhibits the
largest amount of mass loss over this tempera-
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
3755
ture range. Siloxane decomposition at lower
temperatures has also been observed by Lee
et al. in their study of similar polyimide–silox-
ane copolymers.42 The second mass loss at

550 8C is attributed to degradation of poly-
imide backbone. This degradation occurs at
lower temperatures than the parent polyimide,
likely because ionic side-groups and highly flexi-
ble siloxane chains inhibit the formation of a
dense, well-packed polyimide structure.
The proton conductivity of a few representa-
tive samples (N-OB, N-OBP-5 and N-OBP-6)
and Nafion 115 is shown in Figure 6. The IEC
values of SPI samples are significantly higher
than Nafion 115 and are in the order of N-OBP-
5 < N-OB < N-OBP-6. All SPIs, including those
with siloxane segments, exhibit similar proton
conductivities for each humidity condition stud-
ied. This indicates that incorporation of hydro-
phobic siloxane does not strongly affect the
proton conductivity of the sulfonated polyimide
for siloxane content around 1 wt %. It should be
noted that all proton conductivities measured
approach Nafion 115 at high humidity (
90%).
Figure 7 shows the TEM images of N-OB
and N-OBP-5 following a 24-h soak in 0.1 M silver
nitrate solution to obtain contrast. Dark regions
represent hydrophilic ionic domains that con-
tain ion-exchanged silver as suggested by
others.17,43,44 To confirm that the silver cations
were not reduced during the ion-exchange pro-
cess, a film was dipped in 1 M NaBH4 solution (a
reducing agent) and, in seconds, the film changed
black indicating the formation of metallic silver.
Thus, at least part of the silver in the film remains
Figure 6. Proton conductivities of SPIs as a func-
tion of RH.
3756 ZOU AND ANTHAMATTEN
Figure 7. TEM image of N-OB (a) and N-OBP-5 (b). Dark regions depict ionic
domains; contrast was obtained only after ion-exchange of acidified polymers with
Agþ ions.
as Agþ. The observed morphology of N-OB
(without PSX) consists of randomly dispersed
(dark) clusters with diameters ranging from 30 to
50 nm. Dark clusters around 5 nm were also
found, however, these may be part of larger
domains that were sectioned during the microtom-
ing process. Similar morphologies, that is dis-
persed spheres, have been observed by others
using TEM and STEM in studies of other
SPIs.43,44 However these studies all report much
smaller ion cluster sizes, ranging from 5 to 8 nm.
The smaller ionic domains in these studies were
achieved using chemical crosslinking or by incor-
poration of ionic groups as side-chains.
N-OBP-5, with 0.8 wt % polysiloxane seg-
ments, exhibits a much different morphology:
large clusters (diameter
100 nm) are present
that coexist with very small, more dispersed
clusters [< 3 nm, difficult to see in Fig. 7(b)]. A
possible explanation of the larger domains is
that the siloxane segments increase mobility of
ionic groups and they can rearrange to form
larger clusters. The smaller, more dispersed
clusters are attributed to the incompatibility
between the polysiloxane segments and the
ionic-containing polyimides. The smaller clusters
are tightly packed, and may enable ionic path-
ways to form that can facilitate proton trans-
port. Interestingly, the smaller-scale morphology
Journal of Polymer Science: Part A: Polymer Chemistry
is often depleted in an area near the large ionic
domains. This suggests that the larger ionic
domains may grow according to an Ostwald rip-
ening process, locally consuming surrounding
ionic material. Furthermore, this raises the
question whether the observed morphology is in
a kinetically trapped, nonequilibrium state.
To further study the material’s microstruc-
ture, small angle X-ray experiments were
conducted on SPI samples with and without
siloxane segments at room temperature and am-
bient humidity conditions (RH % 45%). The
scattering profile of N-OB (without siloxane)
exhibits a single broad peak at q ¼ 0.29 nm1
[Fig. 8(a)]. This peak corresponds to a periodic
length scale of 21.7 nm, which is significantly
smaller than the interparticle spacing observed
in TEM images such as Figure 7(a). The observed
scattering peak is likely an ‘‘ionomer peak’’ aris-
ing from isotropic scattering of randomly distrib-
uted ion-clusters.45 In Nafion, for example, swel-
ling of ionic clusters in a hydrophobic polymer
matrix has been confirmed using X-ray and neu-
tron scattering models.46 A similar analysis on
sulfonated polyimides is out of the scope of the
present study, but would lead to a better under-
standing of swelling in rigid-rod ionomers.
No correlation peak was observed in all stud-
ies of SPIs containing siloxane segments. An
DOI 10.1002/pola
 SULFONATED POLYIMIDE-POLYSILOXANE COPOLYMER
Figure 8. SAXS profiles of N-OB (a) and N-OBP-5 (b).
example of a scattering profile in N-OBP-5 is
shown in Figure 8(b). This result corroborates
TEM data and indicates that the presence of si-
loxane segments interferes with ion clustering
and ordering.
CONCLUSIONS
We developed a one-pot synthesis of sulfonated
polyimide-polysiloxane (SPI-PSX) segmented
copolymers. The composition of the synthesized
polymers can be determined by careful integra-
tion of 1H NMR peaks. The use of ion-containing
monomers, such as BDSA, inhibits the incorpo-
ration of siloxane groups for the compositions
studied here. SPI-PSX copolymers degrade at
lower temperatures than their parent poly-
imides due to the existence of ionic-side groups
and highly flexible siloxane chains that interfere
with the dense and well-packed polyimide struc-
ture. The presence of hydrophobic siloxane
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
3757
segments does not significantly inhibit water up-
take. This suggests siloxane chains are excluded
from the ion-containing polyimide domains, and
the local ion-density may be increased. SAXS
and TEM experiments suggest that incorpora-
tion of siloxane chains strongly influences poly-
mer morphology, however the proton conductiv-
ity of the material is not strongly affected by
incorporating siloxane segments up to around 1
wt %. Future aims are to fully understand the
interplay between the membrane microstruc-
ture, proton conductivity, ionic content, and
water transport in these and other nanostruc-
tured SPIs.
The authors thank the Department of Chemical Engi-
neering at the University of Rochester for funding
this project. The authors also acknowledge Detlef
Smilgies for assisting with SAXS experiments at the
Cornell High Energy Synchrotron Source (CHESS)
supported by the National Science Foundation under
award DMR-0225180. The authors acknowledge Larry
Kuntz for assistance in setting up the water vapor
sorption apparatus.
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Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola