Desalination, 79 (1990) 125-144

Elsevier Science Publishers B.V., Amsterdam

Anion-Exchange Membranes with Improved

Alkaline Stability
BERND BAUER’, HEINER !TIRATHMANN2 and FRANZ EFFENBERGER3
lFmunhofer-InstitutjZr Grenzjlliihen-und Bioverfahtvnstechnik, NobeIstmjJe 12, 7ooOStuttgart 80
2Universiriit Stuttgart, Institut jZi.r Chemische Verfahrenstechni~ Biiblinger Str. 72, 7ooOStuttgm 1
3Universitiit Stuttgatt, Ins&t fiir Opnische Chemie, Pfaffenwaldring 55, 7000 Stuttgart 80
(Gemany)
(Received April 3,199O; in revised form November 9,199O)

SUMMARY

With the increasing use of electrodialysis in the chemical and biochemical

process industry and for the treatment of industrial waste waters, the
demand for ion-exchange membranes which provide good stability in strong
acid or alkaline solutions has drastically increased. Cation-exchange mem-
branes with adequate chemical stability are available today. However, all
commercial anion-exchanges are unsatisfactory as far as their alkaline
stability is concerned. In this paper the development of anion-exchange
membranes with low electrical resistance, high selectivity and good long-term
stability in strong alkaline solutions is described.

1. INTRODUCI’ION

In the past ion-exchange membranes have mainly been used in electrodi-

alysis for the desalination of brackish water and for the production of table
salt from sea water [l]. In these applications the efficiency of the membranes
is determined mainly by its mechanical stability and its electrical properties.
More recently, however, the use of electrodialysis has been significantly
expanded into other areas such as electroplating waste water treatment or
the chemical or biochemical process industry. Furthermore, new processes
such as the chlorine-alkaline production, alkaline water hydrolysis or the
electrodialytic water dissociation have been developed. In all these processes

ooll-9164/90/$03.50 8 1990 Elsevier Science Publishers B.V.

ion-exchange membranes are required, which, in addition to low electrical
resistance and high ion selectivity, exhibit an excellent chemical stability
especially at low or high pH values and elevated temperatures. In the case
of cation-exchange membranes, the chemical stability can be improved by
perfluorination of the backbone of a sulfonated polymer. Cation-exchange
membranes with adequate chemical stability, such as the Nafion@ or the
Flemion@ membrane are commercially available today. However, compara-
ble attempts with anion-exchange membranes in order to overcome the
above limitations failed when stability in strong alkaline solutions is required
[2]. The purpose of this work is the development of an ion-exchange
membrane with low electrical resistance, high selectivity and excellent long-
term stability in strong alkaline solutions.

2. FUNDAMENTALS

The development of an alkaline resistant anion-exchange membrane

requires an elucidation of the degradation mechanism that takes place at
high pH values. The fact that novel fluorocarbon-type anion-exchange
membranes are still unstable under strong basic conditions [3] suggests that
the functional ion-exchange groups rather than the crosslinked polymer
network undergoes degradation. Therefore, it can be assumed that the
alkaline stability of an anion-exchange membrane is given by the stability of
the weakest link, which in this case are the incorporated positively charged
groups. These fixed ions have to be stabilized against an attack by hydroxide-
ions.
As fixed charges in anion-exchange membranes, the following moieties
can be used:
-NH; -RNH; -R3N+
= R2N+ -R3P + -R2S +

To obtain a low electrical resistance and a high permselectivity, strong base

anion exchangers of the onium-class as shown in Fig. 1 with a high degree
of ionization over a wide pH range have to be introduced into the polymer
network.
Among the different kinds of onium-structures, the quaternary ammom-
urn-ion possesses a considerably higher thermal and chemical stability than
quaternary phosphonium and tertiary sulfonium groups [4]. Besides the
Stevens and the Sommelet-Hauser rearrangement, the degradation in
alkaline solutions is determined by the competition between elimination
versus substitution [5].
 127

Fig. 1. Chemical structure of some common strong basic anion exchange groups.

Ye I -
+ OH-
>=C< + NR,
-Hz0

Fig. 2. Degradation of quaternary ammonium ions by antarafacial EZelimination.

The attack of a hydroxide-ion at the B-H-atom of the quaternary ammoni-

um ion is the final step of the process known as Hofmann degradation which
leads to an elimination of tertiary amine from the neighboring carbon
accompanied by the formation of an olefin as illustrated by the reaction
scheme shown in Fig. 2.
This decomposition belongs to the class of bimolecular elimination
reactions E2 because two reactants are involved in the transition state. One
of the requirements of the concerned EZmechanism is that the hydrogen
atom and the nitrogen group involved in the process are trans or cis to one
another with a dihedral angle of 180” (anti-periplanar or antarafacial) or 0”
(syn-periplanar or suprafacial) respectively. Anti-elimination is greatly
favored over syn-elimination probably because the molecule is in a staggered
conformation and therefore requires less energy to reach the transition state.
When a dihedral angle of 180” cannot be achieved, anti-elimination is
greatly slowed or prevented entirely. The EZelimination with common bases
such as the hydroxide-ion tends to give the most stable alkene, which usually
is the one with the fewest hydrogens or most alkyl groups attached to the
carbons of the double bond. The El-elimination starting with a slow
ionization of the quaternary ammonium-ion as the rate-determining step
followed by the fast attack of the hydroxide-ion at the intermediate carbo-
cation is not taken into account.
128

The most common side reaction competing with elimination is a displace-

ment reaction at the cr-C-atom of the quatemary ammonium-ion. However,
when none of the four groups on the quaternary nitrogen bears a Shydro-
gen, the nucleophilic substitution %2 that yields an alcohol is the only
reaction possible, as indicated in Fig. 3.

OH- /
AS. lx c,-
?:
N+ R3’ * N R3’ + HO--C,
y,...

of L
Fig. 3. Reaction scheme illustrating the degradation of quatemary ammonium ions by the
nucleophilic substitution reaction.

An attackat the a-C-atom by the hydroxide-ion is apparently a bimolecu-

lar reaction with most compounds. The reaction rate depends on the
substrate structure as well as on the stability of the leaving group, and is
therefore usually inverse to the basic@ of the tertiary amine. In general, E2-
elimination is favored over %2-substitution by strongly basic nucleophiles,
bulky nucleophiles and increased substitution at the C)Icarbon.
During the decomposition of benzyltrimethylammonium-groups, no
elimination reaction can take place due to the absence of B-hydrogen atoms.
Anyway, no alkaline stability can be observed because of a rapid substitution
reaction according to Fig. 4 which yields benzyl alcohol as the main product,
benzyldimethylamine and some dibenzylether derived from the benzylalcohol
by dehydration.

FH2 CH2-OH 7.f~

9.1 WW3 N (CH3)2

L J
v
35 % w/w

Fig. 4. Degradation of benzyltrimethylammonium ions under alkaline conditions.

 129

3. EXPERIMENTAL

3.1. Determination of the alkaline stabilityof various qwternury ammonium-

groups
A series of structurally different quaternary benzylammonium salts were
prepared by the Menshutkin-reaction of benzylchloride with various tertiary
amines in acetonitrile as the solvent at room temperature. They were
characterized by their melting points, by NMR, and by C-,H-,N- and Cl-
microanalysis. For the determination of the disintegration rate and the
alkaline stability, respectively, 0.01 N solutions of the quaternary salts in 2N
KOH were prepared. In these solutions the change in ammonium concentra-
tion under nitrogen atmosphere was determined as a function of time by
spectroscopic methods [6] as shown in Fig. 5. To reduce the measuring time,
all experiments were carried out at 160°C. Some selected salts were also
proved at room temperature.

0 50 100 150
reaction time [min]
Fig. 5. Decrease of the concentration of, for example, l-benzyl-1-azonia4azabicyclo-[2.2.2]-
octane hydroxide ions during their exposure to 2N KOH at 160°C.

From the curve shown in Fig. 5 the disintegration rate or the half-time
tt4 was estimated graphically from the half-concentration value. Additionally,
the half-life was calculated mathematically based on the assumption that the
reaction belongs to a pseudo-first-order kinetic by Eqn. (1)

d[;+l - k’ .[Q+]
(1)
130

where [Q’] is the concentration of quaternary ammonium ions [mol/l], t the

reaction time [min], and k’ the reaction constant.
This assumption is possible because the hydroxide ion concentration is
about 200 fold of the ammonium ion concentration.
The integration of Eqn. (1) from t = 0 min to t = x min leads to a very
simple expression to calculate the half time ts from the slope of a diagram
shown in Fig. 6.

ln2
tlh = -
k

where tE is the half-life [min].

-l,o

-1s
0 20 40 60 60

reaction time [min]

Fig. 6. Mathematical calculation of the half-time of, for example, 1-benzyl-1-azonia4azabicyclo-

[2.2.2]-octane hydroxide ions assuming a first-order kinetics.

3.2. Preparation of the anion-exchange membranes [7]

Two different types of anion exchange membranes were prepared: a
microheterogeneous membrane based on an interpenetrating network (IPN)
and a homogeneous type anion-exchange membrane based on a non-
reinforced polymer. For the preparation of the IPN-membrane, a 10% (w/w)
solution of chloromethylated polystyrene in DMA, is d’ persed in a solution
of 20% (w/w) of a given matrix polymer in DMA, usip f an ultraturax stirrer.
The ratio of chloromethylated polystyrene varies from 1.0-2.0 meq/g dry
 131

membrane. Quaternization was obtained by adding 0.55-1.9 meq tertiary

diamine/g dry membrane in DMSO. The clear solution was cast as a 0.4 mm
thick film on a glass plate at room temperature. By evaporating the solvent
during 30 minutes at lZ”C, a 60 pm thick transparent anion-exchange
membrane is obtained. The chloromethylated non-crosslinked polystyrene
used for the membrane preparation contains 5.0-5.25 meq -CH$I/g dry
polymer. The crosslinking density is adjusted by the ratio of the diamine to
the chloromethylated polystyrene.
The homogeneous type anion-exchange membranes are prepared from
chloromethylated polysulfone as both the matrix polymer and ion-exchange
resin. The diamine is added analogously to a 10% (w/w) solution of
chloromethylated polysulfone in DMA,. The functionalized polymer contains
0.8-1.6 meq - CH,Cl/g dry polymer.

3.3. Membrane characterization

The membranes prepared for this study were characterized in terms of
their ion-exchange capacity, their electrical resistance, their swelling and
their permselectivity using standard techniques [8].
The ion-exchange capacity of the membranes was determined by titrating
the fixed groups (- R,N+)Cl- with an aqueous 0.1 N AgN03 solution. For
these tests the membranes are equilibrated for about 24 h in 1 N NaCl and
then rinsed free from chloride with deionized water. To calculate the degree
of swelling from weight difference between the wet and dry membrane, the
samples were equilibrated for 7 d in deionized water. After removing the
surface water from the sample, the wet weight of the swollen membrane
W,r is determined. The sample is then dried at 75°C over phosphorous
pentoxide under reduced pressure until a constant weight Wdr,, is obtained.

Wwet
wt. % gel water = -wdry . I()() (4)
wdry
The electric resistance of ion-exchange membranes is usually reported as
membrane specific area resistance in units of n - cm’. This area resistance
is determined by conductivity measurements in a cell which consists of two
well stirred chambers separated by the membrane sample as shown in Fig. 7.
The cell is filled with a 0.5 N solution of NaCl. The electrical resistance of
the cell is measured with and without a membrane separating the two
chambers. The membrane area resistance is then calculated from the
difference in the conductivity (AC > lk Hz) of the two measurements using
Eqn. (5).
132

1 1
--- (5)
o+m
[ K K0

where RE is the area resistance of the membrane per unit area, K’ tm the
conductivity of the cell and the membrane, and rc”the mean conductivity of
the cell A in the membrane area.

anion-exchange
- membrane -

Fig. 7. Schematic diagram showing the test cell used to determine the electrical resistance of
anion-exchange membranes.

The permselectivity of an ion-exchange membrane is the ability of specific

counter ions to accomplish the total transport of electrical charge through
the membrane, thus excluding all co-ions from the transport. A fast method
for the determination of apparent permselectivities P”+is the static potential
measurement. In this special case the transport of water through the
membrane is not taken into account. As an advantage, the determination of
the potential between two solutions of different concentrations is approxi-
mately independent of any polarization effect at the membrane surface. ‘I’be
actual test system as illustrated in Fig. 8 consists of two cells separated by
the membrane sample. The potential difference across the membrane is
measured using a set of calomel electrodes. For the system consisting of
standardized aqueous solutions of 0.1 N and 0.5 N KC1 at 25”C, this
theoretical potential difference amounts to exactly 36.94 mV. It is calculated
using the following Eqn. (6):
 133

e / Hg2Cl2 / Hg
O.lMKCl H
KC1 (3M)
a
voltmeter
_ [mVl _
:;;:‘.
y.;.:
:;:::
.:i:>.
::::y::.
;> ::
..i..
‘s,..:::,
y;.:::,
.s..z.
LT I.>:,.:.
,?;::, v
;::;,;y
::...:
‘..Z..
:::..,.::,
;:::,;y.

anion-exchange
membrane

Fig. 8. Schematic diagram of the experimental arrangement used to determine the permseleG
tivity of anion-exchange membranes.

AQeo = -~+I (6)

where R is the gas constant, T the absolute tern erature, F the Faraday
constant, z the electrochemical valence, my and m2B the concentrations and
$ and $ the activity coefficients of solute in the two solutions separated by
the membrane.
The apparent permselectivity Pk of the membrane is calculated from the
ratio of the experimentally determined to the theoretically calculated
potential difference AEtheo for a 100% permselective membrane.

p;=- AEexp* 100% (7)

4hco

where AE is the measured potential difference between the two electro-

lytes. The ?&olute value of AE srp is positive for a cation- and negative for
an anion-exchange membrane.
134

3.4. Determination of the alkaline stability of various anion-exchange

membranes
A loss of fixed quaternary ammonium ions will cause a strong reduction
in the ion-exchange capacity and can easily be measured by a strong increase
in the resistance values. Thus the alkaline stability of anion-exchange
membranes was determined by monitoring changes in the electrical resis-
tance and the permselectivity during their exposure to solutions of NaOH.
In connection with a loss of permselectivity and changes in the visual
appearance, the destruction of the membrane matrix can be determined
qualitatively. The results were supported by C-, H-, N- and Cl-microanalysis.

4. RENJLTS AND DISCUSSION

4.1. Alkaline stabiliy of quatemury ammonium groups

With respect to the theoretical considerations on elimination versus
substitution, various types of onium-salts were prepared by Menshutkin-
reaction in acetonitrile. Their half-life and their disintegration rate were
determined at 16O”C, respectively, as shown in Fig. 9.

half-
time

< 0.2

c
- H,C CH, -
\’ @
\/ W-VcH,), A-CH,
-0
\ , 2.1 18.4
o-
H,CACn,

29.1

42.0

Fig. 9. Disintegration rate of different quaternary ammonium ions in 2NKOH at 16O’C under
nitrogen atmosphere. The half-life tH [min] is calculated assuming a kinetics pseudo-first order.
 135

The absolutely highest decay rate (less than 15 s at 160” C) was measured
in conjunction with the immonium-group prepared by alkylation of pyridine
derivates. This structure is immediately converted by a reversible addition-
reaction into the deep-blue pseudo-base followed by an irreversible oxidation
to the pyridone as indicated in Fig. 10. This behavior is expected for all
substituted pyridinium salts as well as, for example, the imidazole and the
acridine moiety.

Q-Q OH- QOH=w-+

I I I
CH3 CH3 CH3 CH3

Fig. 10. Reversible addition of the hydroxide ion to the methylated pyridine followed by an
irreversible oxidation to the N-methyM+yridone.

It could be shown that, in general, due to their higher acidity, the bis-
quaternary salts undergo a rapid elimination according to the monomolecu-
lar El mechanism. Therefore, they usually exhibit a much lower alkaline
stability than the mono-quaternary ammonium groups. The reaction rate of
this El mechanism is determined mainly by the stabilization of the formed
carbocation and by the ionizing power of the solvent. Therefore, no signifi-
cantly enhanced alkaline stability can be expected for the given benzyl-
ammonium salts. The longest half-time (4.7 min at 160°C) was observed for
the benzyl-dimethyl-neo-pen@-system which cannot undergo any elimination
because of the absence of R-hydrogen atoms. Substitution is slowed down by
the neo-pentyl group as a very bad leaving group.
The stability of the mono-quaternary salts can be influenced sterically.
Elimination reactions are prevented by a complete substitution at the l3-
carbon atom or by stiff conformation of the molecule. Six-membered
heterocyclic rings exist mainly in the chair form, in which a strain-free anti-
periplanar conformation of the C,-H with the C,-N bond can be achieved.
For the piperidinium compound this results in a rapid Hofmann elimination
within a half-time of 18.4 min. The benzyltrimethylammonium-group used
in most of the commercial anion-exchange membranes shows likewise a poor
stability although it could not undergo any elimination reaction (29 min at
160°C and 45 h at 8O’C). This behavior is caused by the trimethylamine as
an excellent leaving group in substitution reactions.
The highest alkaline stability was obtained with 1-benzyl-1-azonia4-
azabicyclo-[2.2.2]-octane hydroxide, the mono-quaternary salt of 4,4’-
diazabicyclo-[2.2.2]-octane, which will be abbreviated as DABCO. Assuming
 136

a kinetics pseudo-first order, the half-time at 160°C is 43.6 min and at 80°C
about 85 h.
The absence of elimination could be attributed to the inability of obtain-
ing an anti-periplanar conformation of CB-H and C,-N in the fixed boat
conformation of the bicyclic molecule [9,10] as illustrated in Fig. 11. The
molecule has a cage-like structure with two different internal conformations.
The conformation of maximum symmetry is characterized by carbon-carbon
dihedral angles of 0”. Thus, the carbon atoms are in eclipsed conformation.
Internal steric constraints are such that it is difficult to effect a torsional
distortion greater than about 15”. Therefore, the carbon-carbon dihedral
angle cannot approach the value for either gauche or staggered conforma-
tion.

Fig. 11. Schematic illustration of the molecular conformation in point group symmetry D,,
6/m2 of 4,4’-diazabicycle[2.2.2]-octane in perspective and in projection down the symmetry axis.
The hydrogen atoms are omitted for clarity [ll].

Substitution, on the other hand, is slowed down as a result of an electron-

ic “lone-pair-through-space” interaction between the basic nitrogen and the
quatemary nitrogen. This interaction of the bridgehead nitrogen at the 4
position reduces the acidity of the molecule and decreases the activating
effect of the positive nitrogen towards reactions with hydroxide ions, as
indicated in Fig. 12.

+OH--
-
o-
\ / CH2-OH +

Fig. 12. Degradation of l-benzyl-1-azonia4azabicyclo-[2.2.2]-octane hydroxide by a slow

substitution reaction and the formation of DAJ3CO.
 137

4.2. Anion-exchange membranes with improvkd alkaline stability

Various types of anion-exchange membranes were prepared by quaterni-
zation of a previously chloromethylated polystyrene and polysulfone with the
different tertiary amines and diamines. In the course of the reaction with
monofunctional amines microphase-separation due to a polymer/polymer-
immiscibility results in “snake-in-the-cage”-anion-exchange membranes. The
reaction with diamines yielding ionomers with partially crosslinked side-
chains prevents the phase-separation and produces “interpenetrating-
network”-anion-exchange membranes. The membranes are translucent, an
indication that inhomogeneities, if any, are smaller than 400 nm, the wave-
length of visible light. The apparent ion-exchange capacity of the membranes
varies from OS-l.5 meq/g dry membrane. These measured values are less
than the expected capacities calculated from the amount of the introduced
-CH,Cl groups. The reaction rate for the quaternization with sterically
hindered amines depends on the basicity of the nitrogen atoms, on the
crosslinking of the polymer network and on the stiffness of the main chain.
A limited alkaline stability of the anion-exchange membranes results in
a reduction of the capacity, which is indicated by an increase of the electrical
resistance. In general, the alkaline stability of the membranes is much higher
compared to the monomeric salts. This can be attributed to some diffusional
effects and therefore to a diminished concentration of hydroxide ions in the
region of the positively fixed ions. The stability can further be improved by
a strongly crosslinked matrix polymer. This was shown for a highly cross-
linked anion-exchange resin prepared from styrene/divinylbenzene beads
(ratio of the monomers 80/20). After chloromethylation and quaternization
with 4,4’-diazabicyclo-[2.2.2]-octane, no further degradation below 40” C in
solutions of 2N KOH was observed.
In agreement with the results of the monomeric ammonium-salts, the
membranes prepared by methylation of poly(4-vinylpyridine) in polyvinyl-
idenefluoride as the matrix polymer exhibit the fastest degradation in
alkaline solutions, as shown in Fig. 13. A strong decrease in the permselec-
tivity goes in parallel with an increase of the electrical resistance. The
formation of the pseudo-base immediately diminishes the concentration of
positively charged groups. By this, in alkaline solutions no permselectivity at
all can be observed with pyridinium ion based anion-exchangers. The
decrease of the selectivity measured in solutions of KCl, as indicated in
Fig. 13, is attributed to the irreversible oxidation to the pyridone.
Alkaline stable “interpenetrating network” anion-exchange membranes
were prepared by quatemization of a previously chloromethylated polysty-
rene with 1.4-diazabicyclo-[2.2.2]-octane, the structure of which is shown in
Fig. 14. The crosslinking density is adjusted by the - CH,Cl/DABCO ratio.
138

The membranes were prepared with polyvinylidinefluoride, polysulfone and

polyethersulfone as the matrix polymer.

-
N 120

5
q 100

2 80
8
s 60
w
.C

E 4o
g 2o
m
0
0 10 20 30
exposure to 1 N NaOH at 20 QC (d)

Fig. 13. Typical behavior of methylated poly(4+inylpyridine)-membranes during their exposure

to aqueous alkaline solutions.

Fig. 14. Preparation of interpenetrating network alkaline stable anion-exchange membranes by

quatemization of chloromethylated polystyrene with DABCO.

A further advantage arises from the possibility of stipulating the electrical

and mechanical properties through the density of the polymer network by
the ratio of bi-quaternization, as shown in Table I. An equimolar ratio of
-CH2Cl and DABCO yields not-crosslinked membranes, which means at
x = n in Fig. 14. If the amount of DABCO is reduced to half of the - CH&l
groups, the crosslinking density is defined as lOO%, which corresponds to
X= 0.
 139

TABLE I

Influence of the crosslinking density on the properties of DABCO-anion-exchange

membranes, prepared by quatemization of chloromethylated polystyrene

Degree of crosslinking
Membrane properties
5% 50% 100%

Apparent ion-exchange-capacity [meq/g] 0.87 0.76 0.57

Swelling deionized in water [ %] 25.1 7.3 5.1
Permselectivity 92.5 94.7 95.5
0.1 M/0.5 M KC1
Area resistance 0.36 2.35 4.06
0.5 M NaCl [Q cm21

Following the spectroscopic data and from a C-, H-, N- and Cl-microanal-
ysis, the three membranes show the same theoretical charge density of
0.9 meq/g dry membrane. The concentration of exchangeable groups,
however, is diminished from 0.87 to about 0.57 meq/g dry membrane with
an increase of the relative network density. All data of Table I have been
obtained with hydrophobic polyvinylidenfluoride as the matrix polymer.
Table 1 shows an increase of the resistance from 0.36 @cm2 to about
4 @cm2. The main aspect is an important reduction of the unit volume of
water in the membrane I$20 and by this means a reduction in the co-ion
concentration CFO according to the Donnan-exclusion potential given by
Eqn. (8).

(8)

where C is the electrolyte concentration and y the activity coefficient of the

solute. The subscript co refers to the co-ion and the superscripts o and m
refer to the outer phases and the membrane. CfKed is the concentration of
the fixed ions, which again is given by:

c,axed= Gd +G (9)
P
Hz*
140

This gel water content I$!&) decreases from 25% to about 5% with
increasing network density.

Due to the polymer/polymer immiscibility, it is not possible to prepare

totally not-crosslinked membranes with adequate properties. The most
important aspect, however, is that exposure to basic solutions does not
diminish the degree of crosslinking, as shown in Fig. 15. The degradation of
the bis-quaternary DABCO structure converts the fixed ions into a pipera-
zine system, as indicated in Fig. 16.

biquatern. +OH-
DABCO
- CH $HO

Fig. 15. Preparation of alkaline stable piperazine crosslinks by degradation of the bis-quaternary
DAFSCO structure.

20,o

P
g 15,0
p:
8
E 10,o
ti
3
e

s 5,o
E
2
E
w
0 10 20 30
exposure to 1N NaOH at 20 PC ( d )

Fig. 16. Influence of the crosslinking density on the alkaline stability of different quatemized
DABCO anion-exchange membranes.
 141

The best electrical properties are obtained with the hydrophobic polyvi-
nylidenfluoride (water uptake about 0.03% w/w) as the matrix polymer, but
in alkaline solutions the strong basic quaternary groups catalyze a dehydro-
halogenation of the polymer backbone. The membranes become black and
brittle and from an elementary analysis an increase in the carbon content
could be evaluated. Integrated into a more stable matrix polymer like
polysulfone or polyethersulfone, the anion-exchange membrane did not show
any changes in its mechanical properties. Due to the higher hydrophilicity
of polysulfone (water uptake 0.3%) and polyethersulfone (water uptake
2.3%) the hydratization of the fixed ions in the crosslinked matrix is limited
and thus an increase of the electrical resistance results, as shown in Fig. 17.
Table II shows the properties and the alkaline stability of a non-
reinforced, 60 pm DABCO-polysulfone membrane in comparison to the
commercial AMX (Tokuyama Soda) and MA 3475 (Ionac) anion-exchange
membranes.

TABLE II

Comparison of the properties of the DAF3CO polysulfone membrane with the commercial
membranes from Tokuyama Soda Neosepta@ AMX and IONAC Sybron@ MA-3475.

Membrane properties DABCO AMX MA 3475

Ion-exchange-capacity [meq/g] 1.2 1.3 1.4
Swelling [ %] 8 24 22
Permselectivity [ W] 97.5 90 70
Area resistance [Qcm*] 1.05 2.4 18

The apparent permselectivity of the homogeneous membrane could be

improved to 98% compared to 90% of the AMX. Additionally, the gel water
content of an optimized membrane is reduced to 8%. Nevertheless, with an
apparent ion-exchange capacity of 1.2 meq/g dry membrane, the electrical
resistance is still low.

As indicated in Fig. 19, which shows the alkaline stability of the DABCO-
polysulfone membrane in comparison to the commercially available AMX
anion-exchange membranes, the improved character of the novel DABCO/
PSU-structure can be recognized. The third membrane from IONAC
becomes brittle after 50 days.
142

0 10 20 30 40

eXposore to 1N NaOH at 20 gC ( d)

Fig. 17. Influence of the polymer matrix on the electrical resistance and the alkaline stability
of DABCO anion-exchange membranes.

Fig. 18. Chemical structure of the chloromethylated and quatemized polysulfone DABCO
anion-exchange membrane.
 143

10,o

2
E W
&
tr 8.0

ii
2 40’

9
8 280

3
OS0
0 50 100 150

exposure to 2N NaOH at 40 *C (d)

Fig. 19. Stability of various anion-exchange membranes in aqueous alkaline solutions.

5. CONCLUSION

By means of a mono-quaternization of DABCO, a strong base anion-

exchange group of the onion type is obtained which is useful, for example,
in phase-transfer catalysis in connection with strong alkaline solutions.
Furthermore, the reaction of this DABCO-molecule with a chloromethylated
divinylbenzene-styrene copolymer prepared by emulsion copolymerization
yields an alkaline stable anion-exchange resin useful for chromatographic
separations. Finally, as the most important fact, anion-exchange membranes
prepared by quaternization of a previously chloromethylated polystyrene,
polysulfone, or polyethersulfone with DABCO exhibit excellent chemical
stabilities and electrical properties compared to commercial membranes.

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