Journal of Membrane Science 187 (2001) 255–269

Removal of dilute volatile organic compounds in water

through graft copolymer membranes consisting of
poly(alkylmethacrylate) and poly(dimethylsiloxane) by
pervaporation and their membrane morphology
Tadashi Uragami∗, Hiroshi Yamada, Takashi Miyata
Chemical Branch, Faculty of Engineering and High Technology Research Center, Kansai University, Suita, Osaka 564-8680, Japan
Received 14 March 2000; received in revised form 17 January 2001; accepted 17 January 2001

Abstract
Removal of volatile organic compounds (VOCs) such as benzene and chloroform in aqueous benzene and chloroform
solutions through the poly(methylmethacrylate)-poly(dimethylsiloxane) (PMMA-g-PDMS), poly(ethylmethacrylate)-PDMS
(PEMA-g-PDMS), and poly(n-butylmethacrylate)-PDMS (PBMA-g-PDMS) graft copolymer membranes was investigated
by pervaporation. When aqueous solutions of dilute VOCs were permeated through the PMMA-g-PDMS and PEMA-g-
PDMS membranes, these membranes showed a benzene- and chloroform-permselectivity. Permeation and separation
characteristics of the PMMA-g-PDMS and PEMA-g-PDMS membranes changed drastically at a DMS content of about 40
and 70 mol%, respectively. Permeation rate and VOC-permselectivity of the PBMA-g-PDMS membrane, however, increased
gradually with increasing DMS content, unlike those of the PMMA-g-PDMS and PEMA-g-PDMS membranes. Furthermore,
the transmis- sion electron microscope observations revealed that the PMMA-g-PDMS and PEMA-g-PDMS membranes had
microphase separations consisting of a PDMS phase and a poly(alkylmethacrylate) phase, but the PBMA-g-PDMS membrane
was ho- mogeneous. The permeability and permselectivity for aqueous VOCs solutions through their graft copolymer
membranes in pervaporation are discussed in detail from the viewpoint of their membrane structure, and permselectivity was
analyzed by the solution–diffusion theory. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Graft copolymer membrane; Pervaporation; Permselectivity of VOCs; Microphase-separated structure; Membrane morphology

1. Introduction and ponds. Drinking water sources are often depen-

Volatile organic compounds (VOCs) such as aro-
matic hydrocarbons and chlorinated hydrocarbons
used as washing solvents in the chemical industry
cause soil pollution. Such pollution contaminates
subterranean water and consequently water in rivers
∗
+
Corresponding author. Tel.: 81-6-6368-0805;
+
fax: 81-6-6330-3770.
E-mail address: uragami@ipcku.kansai-u.ac.jp (T. Uragami).
dent on such a contaminated water. Because VOCs
are known to be chemical materials disturbing in-
ternal secretion (environmental hormones) which are
potentially dangerous to human. As such, these
chem- icals have to be removed from a contaminated
water. An activated carbon method, ozone processing
and other methods have been developed to remove
VOCs from water [1]. However, these methods do not
ef- ficiently remove VOCs and the cost of treatment
is high.

0376-7388/01/$ – see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0376-7388(01)00355-6
25 T. Uragami et al. / Journal of Membrane Science 187 (2001) 255–269

Pervaporation is a promising membrane technique in order to develop pervaporation membranes for the
for the separation of VOCs/water mixtures [2–6], as removal of VOCs in water.
pervaporation can be used to separate organic liquid
mixtures such as azeotropic mixtures or close-boiling
point mixtures. Poly(dimethylsiloxane) (PDMS) 2. Experimental
membranes have been studied as VOC-permselective
membranes, because they have a high permselec- 2.1. Materials
tivity and permeability for organic chemicals in
water [7–10]. Brooks and Livingston [11] demon- A PDMS macromonomer of a pendant PDMS
strated removal of chloroform in tap water through a (81 units) (1) was supplied by Toray Dow Corning
hollow-fiber PDMS membrane, which showed high Silicone Co., Ltd. Methylmethacrylate (MMA) (2),
chloroform-permselectivity and permeability. The ethylmethacrylate (EMA) (3) and n-
high VOCs-permselectivity of the PDMS membrane butylmethacrylate (BMA) (4) as comonomers were
is attributable to its stronger affinity for VOCs than purified by dis- tillation under reduced pressure in
for water. Another advantage of the PDMS membrane nitrogen gas. 2,2-Azobis(2-methylpropionitrile)
is high diffusivity of VOCs in the membrane due to (AIBN) recrystal- lized from methanol solution was
its low Tg. The PDMS membrane has some used as an initiator. All other solvents and reagents
disadvantages however, most notably weak were of analytical grade from commercial sources
mechanical strength. Nakagawa et al. have and were used with- out further purification.
introduced cross-linking into the PDMS membrane to
improve its mechanical strength. The introduction of
cross-linking, however, lead to lower diffusivity of
the permeants in the membrane [12].
Multicomponent polymers have certain proper-
ties that cannot be achieved in a homopolymer. It
is well known that multicomponent polymers con-
sisting of immiscible components are characterized
by a microphase separation. Many researchers have
studied the relationship between microphase separa-
tion and the material properties of multicomponent
polymers. There are, however, few reports revealing
the relationship between membrane permselectivity
and microphase separation. Previously, we reported
that graft and block copolymer membranes consisting
of poly(methylmethacrylate) (PMMA) and PDMS
undergo microphase separation, and that their perms-
electivity is strongly influenced by their morphology
[13–17]. The microphase separation phases, consist- 2.2. Copolymerization of PDMS macromonomer
ing of a PMMA phase and a PDMS phase, cause with MMA, EMA and BMA
the high permselectivity and permeability of the graft
and block copolymer membranes without lowering
The PDMS macromonomer and alkylmethacrylate
mechanical strength.
were dissolved in benzene to make a 40 wt.% solu-
In this study, we focused on the microphase-
tion with AIBN, and placed in a glass tube. Copo-
separated structure of two-component polymer
lymerizations were performed for 6 h to synthes-
membranes consisting of PDMS and poly(alkylmeth-
ize poly(methylmethacrylate)-poly(dimethylsiloxane)
acrylate), and investigated the relationship between
(PMMA-g-PDMS), poly(ethylmethacrylate)-PDMS
microphase separation and membrane permselectiv-
(PEMA-g-PDMS), and poly(n-butylmethacrylate)-
ities for aqueous benzene and chloroform solutions
PDMS (PBMA-g-PDMS) under nitrogen gas. The
structures of the obtained copolymers (5) are as chromatograph (GPC), equipped with a TSK-GEL
follows: column (Tosoh Co. Ltd.; G2000HXL, G3000HXL,
G5000HXL). Characterizations of the resulting graft
copolymers are summarized in Table 1.

2.3. Membrane preparation

A prescribed amount of the graft copolymer was

These copolymers were purified by reprecipita-
tion from benzene solution into a 1:2 mixture of n-
hexane and ethanol, and dried in vacuo. The DMS
content in PMMA-g-PDMS, PEMA-g-PDMS, and
PBMA-g-PDMS were determined from 1H NMR
(JEOL; GSX-400spectra) by measuring the integrals
of the peaks assigned to the methyl protons (3.5 ppm)
of the methacrylate and DMS protons (0 ppm) of the
PDMS macromonomer. Average molecular weights
of the copolymers were determined by a gel
permeation
dissolved in benzene at 25◦C at a concentration of 4
wt.% for the preparation of casting solutions. Their
membranes were prepared by pouring the casting so-
lution onto rimmed glass plates and then allowing the
solvent to evaporate completely at 25◦C. The result-
ing membranes were transparent and their thickness
were 80–150 µm.
2.4. Glass transition temperature measurement
The glass transition temperatures (Tg’s) of the
PMMA-g-PDMS, PEMA-g-PDMS, and PBMA-g-
PDMS membranes were determined by a differential
scanning calorimeter (DSC) (Rigaku; TAS-200). The
specimens were heated from about−160 to 180◦C,
with a heating rate of 20◦C/min.

Table 1
Result of the copolymerization of MMA, EMA, and BMA with PDMS macromonomer
Monomer Molecular weighta Polymerb Tg c

Methacrylate Mol% of DMS M¯ w × M¯ n × M¯ w /M¯ n Mol% of DMS Low Middle High

units in feed 10−5 10−5 units in feed
MMA 0 0.89 0.51 1.75 0 – – 128
50 1.74 0.66 2.62 34 −128 – 120
60 1.14 0.60 1.90 52 −125 – 118
70 1.52 0.74 2.04 68 −126 – 112
EMA 0 2.82 2.21 1.28 0 – – 75
10 1.96 1.36 1.43 17 −119 −37 76
30 2.11 1.46 1.43 56 −120 −40 72
50 1.95 1.95 1.55 72 −120 −45 74
60 1.94 1.94 1.50 75 −119 −45 74
70 2.40 1.69 1.42 85 −121 −45 69
BMA 0 2.22 2.12 1.05 0 – – 38
10 1.67 1.24 1.35 16 – −44 –
30 1.63 1.21 1.35 41 – −40 –
60 2.05 1.76 1.17 73 – −40 –
70 2.13 1.83 1.17 86 – −39 –
a
Determined by GPC.
b
Determined by 1H NMR.
c
Determined by DSC.
2.5. Permeation measurements
Pervaporation was carried out under the following
conditions: permeation temperature, 40◦C; pressure
of permeate side,× 1 10−2 Torr. The effective
membrane area was 13.8 cm2. Aqueous solutions of
0.05 wt.% benzene and 0.02 wt.% chloroform were
used as feed solutions. The permeate was collected in
a U-tube at liquid nitrogen temperature. The
permeation rate (kg/m2 h) was determined from the
weight of the per- meate, permeation time, and
effective membrane area (A). In order to facilitate
comparison of permeation rates of membranes with
different thickness, a normal- ized permeation rate
(kg/m h) which is the product of the permeation rate
and the membrane thickness, was used. The benzene
or chloroform concentrations in the feed solutions
and permeants were determined by gas
chromatography (Shimadzu GC-17A) using flame
ionization detector (FID) and capillary column (Shi-
madzu Co. Ltd.: PorapacQ) that was heated to 180◦C.
The separation factor, αVOC/H2O , was calculated from
Eq. (1)
(WVOC/WH2O)P
αVOC/H2O = (1)
(WVOC/WH2 O)F
where (WVOC and WH2O)F are the weight frac- tions
of benzene and water in the feed solution, and
(WVOC and WH2O)P are those in the permeate,
respectively.
2.6. Contact angle measurement
Contact angles for water on the surface of the air-
side of the PMMA-g-PDMS, PEMA-g-PDMS, and
PBMA-g-PDMS membranes were measured by a
contact angle meter (Erma, Model G-I) at 25◦C.
2.7. Degree-of-swelling of membrane
The PMMA-g-PDMS, PEMA-g-PDMS, and
PBMA-g-PDMS membranes, which were completely
dried under reduced pressure at room temperature
and weighed, were immersed into aqueous solutions
of 0.05 wt.% benzene and 0.02 wt.% chloroform in a
sealed vessel at 40◦C. After the weight of the mem-
branes became constant, they were taken out of the
vessel, wiped quickly with filter paper and weighed.
The degree-of-swelling (DS) of the membrane was
determined from Eq. (2):
Ws
DS = (2)
Wd
where W s is the weight of the membrane swollen in
an aqueous solution of benzene or chloroform and W
d is the weight of the dried membrane.
2.8. Sorption selectivity
The composition of benzene or chloroform/water
absorbed by the PMMA-g-PDMS, PEMA-g-PDMS,
and PBMA-g-PDMS membranes was determined
by a previous method [18]. The compositions of
VOC/water mixtures in the membrane and in the feed
gave the sorption selectivity, αsorp.VOC/H2O, expressed
in Eq. (3);
(WVOC/WH2O)M
αsorp.VOC/H2O = 2 (3)
(WVOC/WH O)F
where (WVOC and H2O )F are the weight frac-
W
tions of VOC and water in the feed solution and
(WVOC and WH2O)M are those in the membranes,
respectively.
2.9. Transmission electron micrographs (TEM)
The PMMA-g-PDMS, PEMA-g-PDMS, and
PBMA-g-PDMS membranes were vapor-stained with
an aqueous solution of 5 wt.% RuO 4. The stained
membranes were embedded in epoxy resin and sliced
into thin films (thickness approximately 50 nm) with
a microtome (Leica; Reichert Ultracut E). The
structure of these membranes was observed with a
transmission electron microscope (TEM) (JEOL
JEM-1210) at an accelerating voltage of 80 kV.
3. Results and discussion
3.1. Characterization of graft copolymer membranes
Table 1 summarizes the molecular weights and
com- positions of the PMMA-g-PDMS, PEMA-g-
PDMS, and PBMA-g-PDMS graft copolymers as
deter- mined by GPC and 1H NMR, and the Tg’s of
their
 membranes as determined by DSC. Number-average
molecular weights of PMMA-g-PDMS were in the
range of 50,000–75,000, those of PEMA-g-PDMS
were between 130,000 and 200,000, and those
of PBMA-g-PDMS were between 120,000 and
210,000. The ratio of the weight-average molecu-
lar weight to the number-average molecular weight
(M¯ w /M¯ n ) of PMMA-g-PDMS was greater than
two and that of PEMA-g-PDMS and PBMA-g-
PDMS was less than two. The molecular weight
distribu- tion of PBMA-g-PDMS was very narrow.
Two Tg’s were observed at about
− 128 and
127◦C in the
− PMMA-g-PDMS membranes and at about 73 and
120◦C in the PEMA-g-PDMS membranes. The
observation of two Tg’s in the PMMA-g-PDMS
and PEMA-g-PDMS membranes is attributable to
the fact that the Tg’s of PMMA or PEMA and
PDMS homopolymers are about 128 or 73◦C and
−120 ∼ − 127◦C, respectively. The higher Tg
is due to the MMA or EMA component and the
lower Tg to the DMS component. The presence of
these two Tg’s implies that the PMMA-g-PDMS
and PEMA-g-PDMS membranes had a heteroge-
neous structure. Therefore, it is suggested that the
PMMA-g-PDMS and PEMA-g-PDMS membranes
Fig. 1. DSC curves of the PMMA-g-PDMS, PEMA-g-PDMS, and PBMA-g-PDMS membranes: (a) PMMA-g-PDMS (DMS content:
68 mol%); (b) PEMA-g-PDMS (DMS content: 75 mol%); (c) PBMA-g-PDMS (DMS content: 73 mol%).
have microphase-separated structures. In PBMA-g-
PDMS membranes, however, Tg’s based on the BMA
and DMS components were not observed. Such
obser- vations suggest that the PBMA-g-PDMS
membranes do not form the microphase separation
structure and that the BMA and DMS components
may be misci- ble. On the other hand, in the PEMA-
g-PDMS and PBMA-g-PDMS membranes a peak,
− ∼at−about 39 45◦C on
which is not due to Tg, appeared
the DSC curves of those membranes. This peak is
not due to the second transition caused by the Tg but
rather is due to the first transition as shown in Fig. 1.
3.2. Pervaporation characteristics of the graft
copolymer membranes
Fig. 2 shows the effect of DMS content on the
benzene concentration in the permeate and normal-
ized permeation rate for an aqueous solution of
0.05 wt.% benzene through the PMMA-g-PDMS,
PEMA-g-PDMS, and PBMA-g-PDMS membranes
by pervaporation. Because the permeation rate is sig-
nificantly influenced by the membrane thickness, it is
difficult to compare the permeability of membranes
of different thickness. Therefore, to evaluate the
Fig. 2. Effect of the DMS content on the benzene concentration
Fig. 3. Effect of the DMS content on the chloroform concentration
in the permeate and normalized permeation rate for an aqueous
in the permeate and normalized permeation rate for an aqueous
solution of 0.05 wt.% benzene through the PMMA-g-PDMS (O),
solution of 0.02 wt.% chloroform through the PMMA-g-PDMS
PEMA-g-PDMS (●), and PBMA-g-PDMS (☐) membranes by
(O), PEMA-g-PDMS (●), and PBMA-g-PDMS (☐) membranes
pervaporation.
by pervaporation.

permeability of the graft copolymer membranes,

membranes were gradually enhanced with increas-
we used the normalized permeation rates. All
ing DMS content. The PBMA-g-PDMS membrane
of the graft copolymer membranes increased
did not show dramatic increases in its permselec-
benzene-permselectivity and permeability with in-
tivity and permeability, differing from those in the
creasing DMS content. The benzene-permselectivity
PMMA-g-PDMS and PEMA-g-PDMS membranes.
and normalized permeation rate of the PMMA-g-
Fig. 3 shows the results of pervaporation for
PDMS membrane increased dramatically at a DMS
an aqueous solution of 0.02 wt.% chloroform
content of more than about 40 mol%, and that of the
through the graft copolymer membranes. Similar
PEMA-g-PDMS membrane increased at a DMS con-
to the results for an aqueous benzene solution, the
tent of more than about 70 mol%. On the other hand,
chloroform-permselectivity of PMMA-g-PDMS and
the benzene concentration in the permeate and the
PEMA-g-PDMS membranes increased dramatically
nor- malized permeation rate through the PBMA-g-
at a DMS content of more than about 40 and 70 mol
PDMS
%,
respectively. It is noticeable that the benzene- and
chloroform-permselectivity, and the normalized per-
meation rates for the graft copolymer membranes
changed remarkably at the same DMS content.
These results suggest that the PMMA-g-PDMS and
PEMA-g-PDMS membrane structure changed at the
corresponding DMS content. On the other hand, the
PBMA-g-PDMS membrane showed a gradual
increase in chloroform-permselectivity and
normalized per- meation rate with increasing DMS
content. From the above results, it was found that the
structural change in the PBMA-g-PDMS membrane
with variations in DMS content was quite different
from that of the PMMA-g-PDMS and PEMA-g-
PDMS membranes.

3.3. Chemical structure of the graft copolymer

Fig. 4. Relationship between the DMS content and the contact
membrane
angle for water on the air-side surface of the PMMA-g-PDMS
(O), PEMA-g-PDMS (●), and PBMA-g-PDMS (☐) membranes.
In general, the permselectivity of a polymer mem-
brane is dependent on its chemical and physical
struc- tures, which influences the solubility of
component. Therefore, it is presumed that the air-side
permeants into the membrane and diffusivity of
surfaces of membranes with a DMS content of more
permeants through a membrane. Therefore, we
than 50 mol% have a constant affinity for benzene
investigated the chemi- cal and physical structures of
and chloroform.
the PMMA-g-PDMS, PEMA-g-PDMS, and PBMA-
Fig. 5(a) and (b) show the effect of DMS content
g-PDMS membranes to elucidate the permeation
on the benzene and chloroform concentrations incor-
behavior.
porated into the PMMA-g-PDMS, PEMA-g-PDMS,
The contact angles for water on the air-side sur-
and PBMA-g-PDMS membranes in aqueous solu-
face of the PMMA-g-PDMS, PEMA-g-PDMS and
tions of 0.05 wt.% benzene and 0.02 wt.%
PBMA-g-PDMS membranes as a function of the
chloroform. The benzene and chloroform
DMS content are shown in Fig. 4. The contact angles
concentrations in the PMMA-g-PDMS and PEMA-g-
for water on the air-side surface of all graft
PDMS membranes were highest at particular DMS
copolymer membranes increased with increasing
contents. On the other hand, the benzene and
DMS content. A higher contact angle means that the
chloroform concentrations in the PBMA-g-PDMS
surfaces of the membranes have become more
membrane decreased uniformly with increasing DMS
hydrophobic. The high contact angle is attributable to
content. The difference in the VOC concentrations in
the fact that the hydrophobic PDMS component is
the graft copolymer mem- branes is significantly
localized to the air-side surface. Therefore, it is
dependent upon the affinities of those graft
expected that graft copolymer membranes with a high
copolymer membranes for benzene and chloroform.
DMS content have a stronger affinity for benzene and
To discuss the affinity of the membranes for the
chloroform than those with a low DMS content due
permeants, we tried to calculate the difference in the
to their hydropho- bic surface. As can be seen in Fig.
solubility parameter between VOCs and graft
4, contact angles for water on the air-side surface
copolymers.
became nearly con- stant at a DMS content of more
The effect of DMS content on differences in the
than about 50 mol%. It has been reported that the
solubility parameter (SP) between VOCs and the
contact angle for wa- ter of PDMS membrane was
graft copolymers is shown in Fig. 6. The difference
about 106–107◦ [19]. The observation in Fig. 4
in SP, ∆, was calculated from the solubility
suggests that the surfaces of graft copolymer
parameters of benzene (δbenzene) and the membrane
membranes with a DMS content of more than 50
mol% were covered with a PDMS (δmembrane)
 Fig. 5. Effect of the DMS content on the benzene and chloroform concentration in the PMMA- g-PDMS (O), PEMA-g-PDMS (●), and
PBMA-g-PDMS (☐) membranes for aqueous solutions of 0.05 wt.% benzene (a) and 0.02 wt.% chloroform (b) and the degree-of-swelling
of the PMMA-g-PDMS (O), PEMA-g-PDMS (●), and PBMA-g-PDMS (☐) membranes in 0.05 wt.% benzene (c) and 0.02 wt.%
chloroform
(d) solutions at 40◦C.

using Eq. (4):

∆ = |δbenzene − δmembrane| (4) Table 2

Hansen solubility parameters of solvents and polymers
The solubility parameter, δmembrane, of each graft Material Solubility parameters ((MPa)1/2)
copolymer membrane was calculated from the solubil-
ity parameters and volume ratios of poly(alkylmeth- δd δp δh δ
acrylate) and PDMS. The solubility parameters of H2O 15.5 16.0 42.4 47.9
homopolymers, water and benzene are summarized in Benzene 18.4 0 2.0 18.6
Table 2. Small ∆ means that the membrane has a PMMA 18.8 10.2 8.6 23.1
PEMA 18.8 10.2 4.3 22.1
strong affinity for benzene. The ∆s of the PMMA-g-
PBMA – – – 17.8
PDMS and PEMA-g-PDMS membranes showed a PDMS 15.9 0.10 4.7 16.5
minimum at a DMS content of about 50 and

Fig. 6. Effect of the DMS content on the difference in solu-
bility parameter between benzene and the PMMA-g-PDMS (O),
PEMA-g-PDMS (●), and PBMA-g-PDMS (☐) membranes.
70 mol%, respectively. These results support the sug-
gestion that the affinity of the PMMA-g-PDMS and
PEMA-g-PDMS membranes for benzene is strongest
at about 50 and 70 mol% DMS content, respectively.
On the other hand, the ∆ of the PBMA-g-PDMS
membrane increased uniformly with increasing DMS
content. Changes in the ∆ of the PMMA-g-PDMS,
PEMA-g-PDMS, and PBMA-g-PDMS membranes
with changes in DMS content correspond to changes
in the benzene concentration incorporated into their
graft copolymer membranes, as shown in Fig. 5(a).
These results strongly suggest that the concentration
of VOCs incorporated into the membranes is signif-
icantly dependent on the affinity between the VOCs
and the membranes.
In Fig. 5(a) and (b) it is obvious that is a huge
differ- ence between PEMA-g-PDMS and PBMA-g-
PDMS at low DMS content. It seems that this does
not cor- relate with the measurements of contact
angles in Fig. 4. However, it may be able to explain
as follows. The measurement of contact angles gives
information on only the membrane surface. On the
other hand, the liquid composition adsorbed into the
membrane is governed by both the affinity of
permeants to the membrane and the diffusion of
permeants in the membrane matrix. As mentioned
below a huge dif- ference between the morphology of
PEMA-g-PDMS
and PBMA-g-PDMS membrane was observed. The
difference in such membrane structure may give a
big difference in the liquid composition in the graft
copolymer membrane. We will continuously investi-
gate to make these results clear.
3.4. Physical structure of the graft copolymer
membrane
Fig. 5(c) and (d) show the DS of the PMMA-g-
PDMS, PEMA-g-PDMS, and PBMA-g-PDMS mem-
branes in aqueous solutions of 0.05 wt.% benzene
and 0.02 wt.% chloroform at 40◦C. The degrees of
swelling of all graft copolymer membranes were
very low, regardless of the DMS content. Gener-
ally, the polymer membranes having a strong affinity
for permeants become swollen in the feed solution
[20]. Such swelling of polymer membranes causes a
change in membrane structure during pervaporation.
The graft copolymer membranes used in this study,
however, have a high affinity for benzene and chloro-
form but a very low affinity for water. Therefore, as
aqueous solutions of dilute benzene and chloroform
were used as feed solutions in this study, the degrees
of swelling of the graft copolymer membranes were
very low. These facts suggest that membrane struc-
ture did not change during pervaporation. As can be
seen in changes in Fig. 5, changes in the DS of the
graft copolymer membranes with the DMS content
were very small. Therefore, increases in the permse-
lectivity and permeability with an increasing of DMS
content in the graft copolymer membranes may be
independent of swelling behavior.
The effect of DMS content on the density of the
graft copolymer membranes is shown in Fig. 7. The
density of the PMMA-g-PDMS and PEMA-g-PDMS
membranes decreased dramatically at a DMS content
of about 40 and 70 mol%, respectively, and that of
the PBMA-g-PDMS membrane decreased uniformly
with increased DMS content. In general, the degree
of packing of the molecules in a membrane strongly
influences the permeation rate. For example, when
the degree of packing decreases, the permeation rate
increases [21]. The normalized permeation rate of the
PMMA-g-PDMS and PEMA-g-PDMS membranes
increased dramatically at the corresponding DMS
content as their density decreased. As the density of
the PBMA-g-PDMS membranes decreased
uniformly,

Fig. 7. Effect of the DMS content on the density of the PMMA-g-
PDMS (O), PEMA-g-PDMS (●), and PBMA-g-PDMS
(☐) membranes.
the permeation rate gradually increased as DMS con-
tent increased. Changes in membrane density with
changes in DMS content correspond to changes in
both benzene-permeability and chloroform-
permeability as shown in Figs. 2 and 3. These results
suggest that the density of the graft copolymer
membranes strongly governs their permeability.
In order to discuss membrane structure in more
detail, the morphologies of the graft copolymer mem-
branes were observed by TEM. Fig. 8 shows the
TEM images for cross-sections of the PMMA-g-
PDMS, PEMA-g-PDMS, and PBMA-g-PDMS
membranes. The dark region represents the PDMS
compo- nent stained by RuO4. In the PMMA-g-
PDMS and PEMA-g-PDMS membranes, distinct
microphase separation was observed, but PBMA-g-
PDMS mem- branes shown no microphase
separation. The TEM observations agree with the
results of Tg’s in the DSC measurements of the graft
copolymer mem- branes. Furthermore, it seemed that
the PDMS com- ponent formed a continuous phase at
a DMS content of more than 52 and 72 mol% in
PMMA-g-PDMS and PEMA-g-PDMS membranes,
respectively. As shown in Figs. 2 and 3, the
benzene- and
chloroform-permselectivity of the PMMA-g-PDMS
and PEMA-g-PDMS membranes was enhanced dra-
matically at a DMS content of more than about
50 and 70 mol%, respectively, but the benzene-
and chloroform-permselectivity of PBMA-g-PDMS
membranes was enhanced gradually with increas-
ing DMS content. These results suggest that the
morphology of microphase separation in the graft
copolymer membranes governs their benzene- and
chloroform-permselectivity significantly. Because
benzene and chloroform are mainly permeated
through the continuous poly(alkylmethacrylate)
phases in the PMMA-g-PDMS membranes with less
than about 50 mol% DMS and PEMA-g-PDMS
membranes with less than about 70 mol% DMS, the
diffusivity of benzene and chloroform molecules,
which are larger in molecular size, in these graft
copolymer mem- branes is much lower than the
diffusivity of water molecules. After the PDMS
component forms a con- tinuous phase as DMS
content increases, the such graft copolymer
membranes become more benzene- and chloroform-
permselective due to the enhanced diffusivity of
benzene and chloroform molecules in the continuous
PDMS phase. This is the reason why the benzene-
and chloroform-permselectivity of the graft
copolymer membranes was strongly enhanced with
increased DMS content.
3.5. Mechanism of permselectivity in the graft
copolymer membranes
In general, the separation and permeation charac-
teristics for organic liquid mixtures through polymer
membranes by pervaporation are based on the
solubil- ity of the permeants into the polymer
membrane (sorp- tion process) and the diffusivity of
the permeants in the polymer membrane (diffusion
process) [9,22–24]. It is very important to determine
the sorption selectiv- ity and diffusion selectivity to
elucidate the separation mechanism of aqueous
benzene and chloroform solu- tions through the graft
copolymer membranes. In gen- eral, the separation
factor for mixtures of VOCs and water in
pervaporation was defined by Eq. (5) [25].
αVOC/H2O=αsorp.VOC/H2O · αdiff.VOC/H2O · αevap. (5)
where αevap. is defined as follows:
. Σ
αevap. = PV∗OC γVOC
PH∗ γH2O
2
O
 Fig. 8. TEM micrographs of the PMMA-g-PDMS (a), PEMA-g-PDMS (b), and PBMA-g-PDMS (c) membranes.

where PV∗OC and PH∗2 O are vapor pressures for VOC
and H2O, respectively, and γ VOC and γH2O are their
activity coefficients. In Eq. (5), since the αsorp.VOC/H2O
can be determined by Eq. (3) and the αevap. for an
aqueous solution of 0.05 wt.% benzene is approx-
imately 29.3 (see Appendix A), the αdiff.VOC/H2O can
be calculated from the overall separation factor,
αVOC/H2O, αsorp.VOC/H2O, and αevap. by rearranging
Eq. (5). Even though the αdiff.Bz/H2O for all graft
copolymer membranes is less than unity (for example
at ∼68 mol% DMS in Fig. 9 for the PMMA-g-PDMS
point, αBz/H2O and αsorp.Bz/H2O are about 3730 and
1055, respectively, so αevap. · αdiff.Bz/H2O = 3.54, thus
αdiff.Bz/H2O = 3.54/29.3 = 0.121 (see Appendix A)),
due to the favorable αevap., a good αevap. · αdiff.Bz/H2O
product still results.
In Fig. 9, the αBz/H2O, αsorp.Bz/H2O, and αevap. ·
αdiff.Bz/H2O for an aqueous solution of 0.05 wt.%
benzene as a function of the DMS content in the
PMMA-g-PDMS, PEMA-g-PDMS, and PBMA-g-
PDMS membranes is shown. In this figure, the
αdiff.Bz/H2O of the PMMA-g-PDMS and PEMA-g-
PDMS membranes increased drastically at DMS con-
tents of about 40 and 70 mol%, respectively. These
observations suggest that the relative diffusivity of
benzene in the PMMA-g-PDMS and PEMA-g-
PDMS membranes increased at the corresponding
DMS contents. The PMMA-g-PDMS and PEMA-g-
PDMS membranes with low DMS content showed
low dif- fusion selectivity for benzene. This is
attributable to the larger molecular size of benzene
than water. In addition, the DMS content at which
αdiff.Bz/H2O of the PMMA-g-PDMS and PEMA-g-
PDMS mem- branes changed drastically agreed with
the DMS content at which the PDMS component
changed from a discontinuous phase to a continuous
phase. This indicates that morphological changes in
the mi- crophase separation enhanced the relative
diffusivity of benzene in their membranes. On the
other hand, the αdiff.Bz/H2O of the PBMA-g-PDMS
membrane increased monotonously with increasing
DMS con- tent. The monotonous increase in the
αdiff.Bz/H2O of the PBMA-g-PDMS membrane is due to
the fact that the PDMS component with low Tg
increased in the membrane, and no microphase
separation occurred.
Collectively these observations suggest that the
morphology of the graft copolymer membranes
significantly influences membrane performance in
pervaporation of aqueous VOC solutions. Namely,
the benzene and chloroform-permselectivity of the
PMMA-g-PDMS and PEMA-g-PDMS membranes
increased dramatically at a particular DMS content, Fig. 9. Effect of the DMS content in the PMMA-g-PDMS (O),
and that of the PBMA-g-PDMS increased gradu- PEMA-g-PDMS (●), and PBMA-g-PDMS (☐) membranes on
ally with DMS content. The PMMA-g-PDMS and their separation factor (a), sorption selectivity (b), and diffusion
PEMA-g-PDMS membranes, in particular, showed a selectivity (c) for an aqueous solution of 0.05 wt.% benzene.
higher benzene- and chloroform-permselectivity as
the PDMS component changed from a discontinuous
phase to a continuous phase.
3.6. Permeation mechanism
The permeation mechanism of aqueous VOCs
solu- tions through the graft copolymer membranes
can be explained by a tentative model shown in Fig.
10. Ben- zene and chloroform are more preferentially
incorpo- rated into the graft copolymer membranes
with every DMS contents, because PMMA, PEMA,
PBMA, and PDMS have a much stronger affinity for
benzene and chloroform than water. Since the
surfaces of the graft copolymer membranes with a
DMS content of more than 50 mol% are covered with
the PDMS compo- nent, the concentrations of
benzene and chloroform on the surfaces of the graft
copolymer membranes are
Fig. 10. Tentative model for separation process (a) and diffusion process (b) of dilute aqueous VOCs solutions through the PMMA-g-PDMS,
PEMA-g-PDMS, and PBMA-g-PDMS membranes.
saturated at a DMS content of more than 50 mol%.
However, the benzene- and chloroform-
permselectivity of the PMMA-g-PDMS and PEMA-
g-PDMS mem- branes changed dramatically at DMS
contents of about 40 and 70 mol%, respectively. This
is attributable to a drastic change in the diffusivity of
permeants based on structural changes in the graft
copolymer membranes. The TEM observation
demonstrated that the selectiv- ity and the
permeability of the PMMA-g-PDMS and PEMA-g-
PDMS membranes are strongly enhanced as the
PDMS component in the PMMA-g-PDMS and
PEMA-g-PDMS membranes begins to form a
continuous phase. Our previous studies have made
it clear that graft copolymer membranes for the sep-
aration of aqueous ethanol solutions changed from
water-permselective to ethanol-permselective at the
DMS content at which their microphase-separated
structure changed from a discontinuous PDMS phase
to a continuous PDMS phase [13–17]. The pervapo-
ration results of the graft copolymer membranes for
aqueous VOC solutions in this study are supported
by similar observations in previous studies. Table 2
suggests that the PDMS component has a stronger
affinity for benzene than the PMMA or PEMA com-
ponents. Moreover, as the Tg of PDMS is lower
than that of either PMMA or PEMA, it is presumed
that the permeants diffuse more easily in the PDMS
phase than in the PMMA or PEMA phase [13–17].
When the PDMS component in their graft copolymer
membranes forms a continuous phase, benzene and
chloroform are preferentially incorporated into a con-
tinuous PDMS phase with a high affinity for benzene
and chloroform. Consequently, the high benzene and
chloroform-permselectivity for the PMMA-g-PDMS
and PEMA-g-PDMS membranes is significantly
dependent on both the sorption of benzene and
chloroform into a continuous PDMS phase and the
diffusivity of these molecules in this PDMS phase.
Although the PBMA-g-PDMS membranes showed
benzene- and chloroform-permselectivity, they did
not demonstrate a microphase separation. As a result,
the permeation and separation characteristics of the
PBMA-g-PDMS membranes were quite different
from those of the PMMA-g-PDMS and PEMA-g-
PDMS membranes. This study revealed that the
morphology
of multicomponent polymer membranes has a strong
influence on their permeability and permselectivity.
4. Conclusions
The graft copolymer membranes consisting of
PMMA, PEMA, and PBMA with PDMS showed
benzene and chloroform-permselectivity in the sepa-
ration of aqueous solutions containing a very small
amount of benzene and chloroform. Benzene- and
chloroform-permselectivity was enhanced with in-
creasing DMS content. In particular, the permselec-
tivity of the PMMA-g-PDMS and PEMA-g-PDMS
membranes changed drastically at DMS con-
tents of 40 and 70 mol%, respectively. Investiga-
tions into the chemical and physical structure of
these graft copolymer membranes revealed that
their permselectivity was significantly influenced
by the microphase-separated structure. When the
PDMS component in the graft copolymer mem-
branes with microphase separation formed a con-
tinuous phase, the membranes showed a high
benzene- and chloroform-permselectivity. The high
benzene and chloroform-permselectivity of the
microphase-separated membranes was due to high
diffusivity of benzene and chloroform in the continu-
ous PDMS phase.
Acknowledgements
This work was supported by a Grant-in-Aid for
Sci- entific Research (C) (no. 12650892) from the
Ministry of Education, Science, Sports and Culture,
Japan.
Appendix A
We took the azeotropic composition at 69 ◦C for
benzene/water and fit the Carlson and Colburn modi-
fication to the Van Laar equation:
Arx2
log γBz = Σ H2O Σ
2
r r
(A /B )xBz + xH 2O
and
Brx2
Bz
log γBz = Σ Σ2
r r
(B /A )xH2O + xBz
for Ar = 0.946 and Br = 1.48 as effectively constant
values over the range 69 → 25◦C, where Ar and Br are
constants. γ Bz and γH2O are activity coefficients for
benzene and water, respectively. xBz and xH2O are
mole fraction for them.
The vapor pressure of benzene, PB∗z and that of
wa- ter, PH∗2 O are 182 and 54.8 mmHg,
respectively, and a mole fraction of benzene for the
weight fraction of
0.0005 is 0.000115. The γ Bz and γH2O at that com-
position can be estimated by the above numbers as
follows:
γBz = 8.828
γH2O = 1.00017
These numbers seem reasonable, since benzene
does not like water and is essentially at “infinite
dilution” where log γ Bz = Ar(1.0), or γ Bz = 8.83.
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