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Army Research Laboratory
Aberdeen Proving Ground, MD 21005-5069
Yossef A. Elabd
Department of Chemical Engineering
Drexel University
Eugene Napadensky
Weapons and Materials Research Directorate, ARL
Abstract
In this study, a triblock copolymer, poly(styrene-isobutylene-styrene), was sulfonated to eight different levels ranging from 0.36 to
2.04 mequiv./g (13 to 82 mol% of styrene; styrene is 19 mol% of the unsulfonated block copolymer). These sulfonated polymers were
characterized with elemental analysis and infrared spectroscopy to confirm sulfonation and determine accurate sulfonation levels. Infrared
analysis revealed four additional stretching vibrations as a result of sulfonation. Also, a linear relationship between absorbance at 1006 cm21
(stretching of the aromatic ring in styrene caused by the para-substituted sulfonic acid) and sulfonation level (measured by elemental
analysis) was found. The density and water solubility of all the sulfonated polymers were measured and increased with increasing sulfonation
level, as high as 1.31 g/cm3 and 351 wt%, respectively. In addition, a sulfonated triblock copolymer at 79 mol% sulfonation was neutralized
with a cesium cation and revealed an increase in density, but a reduction in water solubility. This study demonstrates the resulting unique
properties of sulfonated styrene-based block copolymers at higher ion-exchange capacities than previously reported.
q 2004 Published by Elsevier Ltd.
Keywords: Block copolymer; Ionomer; Polyelectrolyte
and ionomers, in which only one of the blocks is sulfonated (Mallinckrodt), methanol (EM Scientific, HPLC Grade),
or ionic. In theory, a sulfonated block copolymer should self and water (J.T. Baker, HPLC grade).
assemble into a three-phase morphology in the solid state. In
this state, different blocks phase segregate as a result of 2.2. Sulfonation
thermodynamic incompatibilities, while phase segregation
will occur within the ionic block as a result of electrostatic Sulfonation of SIBS was performed in solution with
interactions among ion pairs. A study by Wiess et al. [10], acetyl sulfate as the sulfonating agent. Acetic anhydride
using X-ray scattering on sulfonated poly(styrene-(ethyl- reacts with sulfuric acid to form acetyl sulfate (sulfonating
ene-co-butylene)-styrene), confirmed this three-phase mor- agent) and acetic acid (by product) and removes excess
phology with a Bragg spacing of 3 –4 nm for the ionic water (anhydrous conditions are required for sulfonation)
domains and 20 – 30 nm for the polystyrene domains. (Fig. 1(a)). The sulfonation reaction produces sulfonic acid
Sulfonated block copolymers are intriguing materials substituted to the para-position of the aromatic ring in the
because of the combination of their different block (ionic styrene block of the polymer (Fig. 1(b)).
and non-ionic) properties and their ordered ionic structures. An example of the sulfonation procedure used in this
Several sulfonated block copolymer studies of interest study is as follows: a 10% (w/v) solution of SIBS (50 g) in
include sulfonated poly(4-vinylpyridinium-styrene-4-vinylpyr- methylene chloride (500 ml) was prepared. The solution
idinium) [11], sulfonated poly(styrene-(ethylene-co-butylene)- was stirred and refluxed at approximately 40 8C, while a
styrene) [12], and sulfonated poly(styrene-isobutylene-styrene) specified amount of acetyl sulfate in methylene chloride was
[13]. However, these investigations focused only on the slowly added to begin the sulfonation reaction. Acetyl
sulfonation and characterization of styrene-based block sulfate in methylene chloride was prepared prior to this
copolymers at low sulfonation levels or low ion contents reaction by cooling 150 ml of methylene chloride in an ice
(below 20 mol% sulfonation of the styrene block). Recently, bath for approximately 10 min. A specified amount of acetic
several studies have explored the sulfonation and charac- anhydride and sulfuric acid was then added to the chilled
terization (transport properties) of block copolymers at methylene chloride under stirring conditions. Sulfuric acid
higher sulfonation levels, as high as 60 mol% sulfonation, was added approximately 10 min after the addition of acetic
and have shown that these sulfonated block coplymers are anhydride with acetic anhydride in excess of a 1:1 mole
comparable in performance to Nafion [14 – 16]. Similarly, ratio. This solution was then allowed to return to room
our laboratory has investigated the performance of sulfo- temperature before addition to the reaction vessel.
nated poly(styrene-isobutylene-styrene) in regards to fuel After approximately 5 h, the reaction was terminated by
cell applications [17 – 18]. slowly adding 100 ml of methanol. The reacted polymer
In our laboratory, the sulfonation of block copolymers is solution was then precipitated with deionized water. The
of interest for applications to both fuel cells and textiles precipitate was washed several times with water and
(protective breathable clothing). Both applications require methanol, separately, and then dried in a vacuum oven at
resistance to organics, while still providing high transport of 50 8C for 24 h. This washing and drying procedure was
protons (fuel cells) and water (breathable clothing). The repeated until the pH of the wash water was neutral. After
objective of this investigation is to examine the properties of this process, the final polymer yield was approximately 98%
a sulfonated styrene-based block copolymer, poly(styrene- on average. This sulfonation procedure was repeated with
isobutylene-styrene), at higher sulfonation levels (above different amounts of acetyl sulfate to produce several
80 mol% sulfonation of the styrene block or 2 mequiv./g) sulfonated polymers with various levels of sulfonation or
than have previously been reported in order to produce ion-exchange capacities (IECs). Hereafter, the sulfonated
materials with increased proton and water transport rates. triblock copolymers are referred to as S-SIBS-# (S-SIBS
represents sulfonated poly(styrene-isobutylene-styrene) and
the succeeding number, #, refers to the mol% sulfonation).
2. Experimental The mol% sulfonation is defined as:
moles of sulfonic acid
2.1. Materials mol% ¼ 100 ð1Þ
moles of styrene
Poly(styrene-isobutylene-styrene) (SIBS) triblock copo- and the IEC is defined as the mille-equivalents of sulfonic
lymer was provided by Kuraray Co., Ltd, Tsukuba research acid per gram of polymer (mequiv./g).
laboratories, (sample name-TS-3000S, lot. no. 990215) with After sulfonation and washing of each polymer, the
the reported properties: 19.36 mol% (30.84 wt%) styrene, S-SIBS samples were dissolved in a mixed solvent of
0.95 specific gravity, Mw ¼ 71:920 g=mol; Mn ¼ 48:850 toluene/hexanol (85/15, w/w) with concentrations ranging
g=mol; and PDI ¼ 1.47. Other chemicals used in this study from 5 to 2.5% (w/v) and solution cast in open Teflonw Petri
are as follows: toluene (VWR), hexanol (J.T. Baker), dishes for approximately 1 week at ambient conditions.
methylene chloride (EM Science, HPLC Grade), sulfuric Solvent-cast membranes were then annealed in a vacuum
acid (Fisher Scientific, Assay 95.4%), acetic anhydride oven at 50 8C for an additional two weeks to remove any
Y.A. Elabd, E. Napadensky / Polymer 45 (2004) 3037–3043 3039
Fig. 1. Sulfonation reactions: (a) preparation of sulfonating agent (acetyl sulfate): acetic anhydride reacts with sulfuric acid to form acetyl sulfate and acetic
acid, (b) sulfonation reaction: SIBS reacts with acetyl sulfate to form S-SIBS, where the styrene block is randomly sulfonated (sulfonic acid substituted in the
para-position of the aromatic rings).
S-SIBS-0 0 0
S-SIBS-13 12.50 0.36
S-SIBS-29 29.23 0.81
S-SIBS-42 41.95 1.13
S-SIBS-48 48.16 1.28
S-SIBS-54 53.68 1.41
S-SIBS-70 70.14 1.78
S-SIBS-79 79.05 1.97
S-SIBS-82 82.41 2.04
a
S-SIBS ¼ sulfonated poly(styrene-isobutylene-styrene). Fig. 3. Reaction efficiency versus sulfonation level in S-SIBS.
Y.A. Elabd, E. Napadensky / Polymer 45 (2004) 3037–3043 3041
Fig. 4. Infrared spectra for S-SIBS-0 and S-SIBS-79. Four new bands Fig. 6. Infrared spectra for S-SIBS-79 and S-SIBS-79-Cs. A shift in the
(indicated with arrows) are evident in the sulfonated polymers, 1156, 1127, vibrational band (1156–1183 cm21) is indicated by the arrows.
1034, 1006 cm21, representing the stretching vibrations associated
sulfonation. more logical. However, there is no literature to support this
view.
and sulfonation level (determined from EA) in the polymer Also, a shoulder appears in the S-SIBS-79-Cs infrared
is shown in Fig. 5. spectra around 1210 cm21, which is also seen in the
Additionally, the infrared spectra of S-SIBS at 79 mol% S-SIBS-79 spectra in the range of 1210 – 1230 cm21.
sulfonation in both acid form (S-SIBS-79) and neutralized Other sources [19 – 20] have suggested two bands
with a cesium cation (S-SIBS-79-Cs) are shown in Fig. 6. A (a doublet) associated with the asymmetric stretching of
noticeable difference between the two spectra is a shift the sulfonate group, with a second band located around
(from 1156 to 1183 cm21) and an increase in intensity of the 1200 – 1230 cm21. The extra band in these two spectra,
asymmetric stretching band of the sulfonate group. It is shown in Fig. 6, may be associated with a second mode of
unclear why the asymmetric stretching vibration changes asymmetric stretching of the sulfonate group, but its exact
while other stretching modes associated with the sulfonate location is difficult to determine in this study due to a band
group remain unaltered. One possible explanation is that conflict with the band at 1230 cm21 associated with the
the stretching mode at 1156 cm21 does not represent the unsulfonated polymer (Fig. 4).
asymmetric stretch of the sulfonate group, but rather the
sulfonate anion attached to the aromatic ring of styrene. If 3.3. Density
the band assignment between 1127 and 1156 cm21 were
reversed, this band shifting due to neutralization may seem Fig. 7 shows the density of S-SIBS polymers as function
of sulfonation level measured with helium pycnometry. The
polymer density increases from 0.95 to 1.31 g/cm3 with
increasing sulfonation level. Polymer density increases even
[10] Weiss RA, Sen A, Pottick LA, Willis CL. Block copolymer ionomers: sulfonated polystyrene-(ethylene-butylene)-styrene triblock proton
2. Viscoelastic and mechanical properties of sulfonated poly(styrene- exchange membranes. J Membr Sci 2003;214:245.
ethylene/butylene-styrene). Polymer 1991;32:2785. [17] Elabd YA, Napadensky E, Sloan JM, Crawford DM, Walker CW.
[11] Gouin JP, Williams CE, Eisenberg A. Microphase structure of block Triblock copolymer ionomer membranes. Part I: methanol and proton
ionomers. 1. Study of molded styrene-4 vinylpyridinium ABA blocks transport. J Membr Sci 2003;217:227.
by SAXS and SANS. Macromolecules 1989;22:4573. [18] Elabd YA, Walker CW, Beyer FL. Triblock copolymer ionomer
[12] Weiss RA, Sen A, Willis CL, Pottick LA. Block copolymer ionomers: membranes. Part II: structure characterization and its effects on
1. synthesis and physical properties of sulfonated poly(styrene- transport properties and direct methanol fuel cell performance.
ethylene/butylene-styrene). Polymer 1991;32:1867. J Membr Sci 2004;231:181.
[13] Storey RF, Chisholm BJ, Lee Y. Synthesis and mechanical properties [19] Lin-Vien D, Colthup NB, Fateley WG. The handbook of infrared and
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[14] Edmondson CA, Fontanella JJ, Chung SH, Greenbaum SG, Wnek GE.
[20] Pereira MR, Yarwood J. ATR-FTIR spectroscopic studies of the
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