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Journal of Membrane Science 315 (2008) 20–27

Polyamide thin film composite membranes prepared from isomeric

biphenyl tetraacyl chloride and m-phenylenediamine
Lei Li a,b , Suobo Zhang a,∗ , Xiaosha Zhang a , Guodong Zheng a
a State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry,
Chinese Academy of Sciences, Changchun 130022, China
b Graduate School of Chinese Academy of Sciences, Beijing 100049, China

Received 5 October 2007; received in revised form 22 January 2008; accepted 1 February 2008
Available online 21 February 2008

Abstract
Three novel of isomeric tetra-functional biphenyl acid chloride: 3,3 ,5,5 -biphenyl tetraacyl chloride (mm-BTEC), 2,2 ,4,4 -biphenyl tetraacyl
chloride (om-BTEC), and 2,2 ,5,5 -biphenyl tetraacyl chloride (op-BTEC) were synthesized, and used as new monomers for the preparation of the
thin film composite (TFC) reverse osmosis (RO) membranes through interfacial polymerization with m-phenylenediamine (MPDA). The results of
membrane performance test showed that membranes prepared from om-BTEC and op-BTEC had higher flux at the expanse of rejection compared
with membranes prepared from mm-BTEC. The chemical composition on the active layer was characterized by attenuated total reflectance infrared
(ATR-IR) and X-ray photoelectronic spectroscopy (XPS), and the results showed that the content of carboxylic acid on the membrane surface
prepared from mm-BTEC are higher than these prepared from op-BTEC and om-BTEC. It seemed that all the difference containing: the membrane
performance, the chemical composition on the active layer, hydrophilicity, and the surface morphology might come from the different structure
and reactivity of the tetraacyl chloride monomers.
© 2008 Elsevier B.V. All rights reserved.

Keywords: Reverse osmosis; Thin film composite; Polyamides; Selectivity

1. Introduction cross-linkers such as trimesoyl chloride (TMC), isophthaloyl

Reverse osmosis separation has attracted significant research
attention as an economic process in the field of water desalina-
tion, ultra-pure water production, and waste-water treatment [1].
Thin film composite (TFC) membranes fabricated via interfacial
polymerization (IP) have been proved to be the most success-
ful RO membranes. They typically consist of three structural
components: (1) top ultra-thin skin polyamide layer; (2) middle
polysulfone porous support; (3) bottom non-woven polyester
fabric. In TFC membranes, the active skin layer is the key
component, which controls mainly the separation properties
of the membrane, while the support layer gives the mem-
brane necessary mechanical properties. The materials used to
produce the skin layer included polyamides from aliphatic
or aromatic diamine [2–5], poly(aminostyrene) [6,7] and the
∗ Corresponding author.
E-mail address: sbzhang@ciac.jl.cn (S. Zhang).
chloride and terephthaloyl chloride. Other polymers such as
polyurea, polyurea-amide, polyether-amides etc. [8–13] had
been investigated as candidate TFC materials. Among these
polymers, the cross-linked aromatic polyamide which is pro-
duced by the interfacial polymerization of m-phenylenediamine
(MPDA) and TMC is the most successful commercial
product.
The TFC membrane performances of polyamides are influ-
enced by several structural and processing variables, such
as primary polymer structure (m/p-phenylene units), casting
solution composition, evaporation period, post-annealing treat-
ments, etc. In terms of polymer structure, it was believed that
several factors could influence the membrane performances,
such as monomer size, solubility, shape and reactivity [14].
Over the past decades a body of knowledge had been devel-
oped which related polymer structure to its solute permeability
and other physical properties. Mickols, for example patented
the work on flux enhancement by varying the type of amine
employed [15]. Roh had studied the effect of the isomeric

0376-7388/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2008.02.022
 L. Li et al. / Journal of Membrane Science 315 (2008) 20–27
Fig. 1. Structures of the acyl chloride monomers.
diamine monomers on membrane performances [16]. It was
revealed that the meta-positioned polyamide (TMC/MPDA)
had higher hydrophilicity and greater molecular chain mobil-
ity than the para-positioned polyamide (TMC/PPDA), hence,
resulting in higher water flux. Moreover, Kim et al. had stud-
ied how membrane performance was related to the molecular
structure of aromatic polyamides and the incorporation of
poly(p-aminostyrene) or poly(m-aminostyrene) to the aromatic
polyamides for fabricating active skin layer affects the mem-
brane performance [6,7].
Since the IP process is diffusion controlled in the organic
layer [17], the effect of organic phase reactant is likely to
have a great impact on membrane performance. In previous
paper, we reported that the preparation of polyamide TFC mem-
branes from 3,3 ,5,5 -biphenyl tetraacyl chloride (I, mm-BTEC)
and MPDA, and found that the membrane had lower flux and
higher rejection compared with the membrane prepared from
TMC/MPDA [18]. As a continuation of this study, the other
two isomeric compounds: 2,2 ,4,4 -biphenyl tetraacyl chloride
(II, om-BTEC) and 2,2 ,5,5 -biphenyl tetraacyl chloride (III,
op-BTEC) were synthesized and used as the monomers for
the preparation of polyamide TFC membranes (Fig. 1). In this
paper, we reported the preparation of isomeric biphenyl tetraa-
cyl chloride-based polyamide RO membranes. The relation
between the acyl chloride monomer structure and the mem-
brane performance, the chemical composition of the active
layer, hydrophilicity, surface morphology were discussed in this
paper.
2. Experimental
2.1. Synthesis of monomers
2.1.1. Materials
Reagent grade anhydrous NiBr2 was dried at 250 ◦ C under
vacuum. Triphenylphosphine (PPh3 ) was recrystallized from
hexane. Powdered (100 mesh) zinc was stirred with acetic
acid, filtrated, washed thoroughly with diethyl ether, and dried
under vacuum. N,N-dimethylacetamide (DMAc) was stirred
over phosphorous pentoxide for 5 h, then distilled under reduced
pressure, and stored over 4 Å molecular sieves. Copper pow-
dered (shot 1–10 mm) was purchased from Acros. Other reagents
and solvents were obtained commercially and used without fur-
ther purification.
21
2.1.2. Synthesis of 2,2 ,5,5 -tetramethyl-1,1 -biphenyl
The 2,2 ,5,5 -tetramethyl-1,1 -biphenyl was prepared from
1-bromo-2,5-dimethylbenzene by following the literature pro-
cedure [19]. 1 H NMR (CDCl3 , ppm): δ 7.145–7.120 (d, 2H),
7.065–7.040 (d, 2H), 6.915 (s, 2H), 2.328 (s, 6H), 2.013 (s, 6H).
2.1.3. Synthesis of 2,2 ,5,5 -biphenyl tetracarboxylic acid
The 2,2 ,5,5 -biphenyl tetracarboxylic acid was prepared by
following the literature procedure [20]. 1 H NMR (DMSO-d6 ,
ppm): ␦8.00 (m, 4H), 7.68 (s, 2H).
2.1.4. Synthesis of 2,2 ,5,5 -biphenyl tetraacyl chloride
The 2,2 ,5,5 -biphenyl tetracarboxylic acid (3.3 g, 10 mmol)
was reacted with SOCl2 (7.3 ml, 100 mmol) for 8 h under
reflux. After evaporation of SOCl2 , the residue was recrystal-
lized from hexane to give the final product. 1 H NMR (CDCl3 ,
ppm): δ 8.459–8.431 (d, 2H), 8.371–8.343 (dd, 2H, J = 1.5 Hz),
7.943–7.938 (d, 2H, J = 1.5 Hz). IR (KBr, cm−1 ): 1767, and
1743. Anal. Calcd. for C16 O4 Cl4 H6 : C, 47.52%, H, 1.49%, Cl,
35.15%. Found: C, 47.54%, H, 1.50%, Cl, 35.11%.
2.1.5. Synthesis of 2,2 ,4,4 -biphenyl tetraacyl chloride
The 2,2 ,4,4 -biphenyl tetraacyl chloride (om-BTEC) was
prepared from 1,3-dimethyl-4-bromobenzene dicarboxylate
following the literature [21]. 1 H NMR (CDCl3 , ppm):
8.987–8.981 (d, 2H, J = 1.8 Hz), 8.366–8.339 (dd, 2H,
J = 1.8 Hz), 7.311–7.284 (d, 2H,). IR (KBr, cm−1 ): 1765, and
1742. Anal. Calcd. for C16 O4 Cl4 H6 : C, 47.52%, H, 1.49%, Cl,
35.15%. Found: C, 47.50%, H, 1.48%, Cl, 35.17%.
2.2. Preparation of the composite membrane
2.2.1. Preparation of microporous polysulfone support
membrane
To fabricate the TFC membrane, a support substrate com-
posed of microporous polysulfone was first prepared by the
following procedures. A solution of 16.5% (by weight) polysul-
fone (Udel P-3500, U.S. Amono Comp), 13.5% ethyleneglycol
monomethyl ether (EGM), 0.03% dodecyl sulfonic acid sodium
salt (DDS) and DMF 69.97% was cast onto a glass plate with
a polyester non-woven fabric using a 0.29-mm knife gape. The
plate was immediately immersed in a water bath at room tem-
perature in one smooth motion. Within 30 s the PS gelled into a
white microporous sheet, and the top face was used as a support
surface for the TFC membrane.
2.2.2. Fabrication of thin film composite membrane
The active skin layer of the composite membrane was
prepared by interfacial polymerization technology. First, the
aqueous solution containing MPDA (2%, w/v), triethyl amine
(TEA) (1%) and dodecyl sulfonic acid sodium salt (DSS)
(0.05%, w/v) was prepared with pH 10 adjusted by camphor sul-
fonic acid. Then, the aqueous solution was poured on top of the
support membrane and allowed to soak in 3 min. Excess solution
was drained from the dip-coated surface and air-dried at room
temperature until no remaining liquids. Afterwards, the organic
22 L. Li et al. / Journal of Membrane Science 315 (2008) 20–27
phase with acyl chloride (0.1%, w/v) in hexane was poured on
the top of the support membrane for 20 s. After removing the
excess organic solution, the membrane was heated in an oven
at 60 ◦ C for further polymerization. Finally, the membrane was
rinsed with DI water and stored in 1% NaHSO3 solution. All
above operations were performed in an assembly clean room.
2.3. Performance testing
The membrane samples were checked carefully under a flu-
orescent lamp to avoid some obvious defects before test. All
tests for RO performance were conducted at 2.0 MPa using a
2000 ppm NaCl solution at room temperature in cross-flow cells.
Circular membrane samples were placed in the test cell with the
active skin layer facing the incoming feed. The effective mem-
brane area (for each cell) was around 19 cm2 . The membranes
were initially subjected to pure water with pressure of 2.0 MPa
for 4 h prior to performing the RO test experiments.
The water flux was determined by direct measurement of
the permeate flow (l/(m2 h)). The salt rejection rate was mea-
sured by the salt concentration in the permeate obtained through
measurements of the permeate and the feed using a conduc-
tance meter (Elmeiron conductivity meter CC-501, Poland). The
desalination rate was calculated by using the following equation:
 
cp
Rj (%) = 1− × 100
cf
in which cp (mg/l) is the permeate concentration and cf (mg/l)
is the feed concentration.
All membrane samples were prepared and tested in at least
duplicated with a total of three membranes tests for RO perfor-
mance, results of which have been averaged.
2.4. Characterization
2.4.1. Characterization of monomers
The monomers were identified by elemental analysis, such as
C, H, and Cl. The 1 H NMR spectra were measured at 300 MHz
on a AV300 spectrometer. The FT-IR spectra were obtained with
a Bio-Rad digilab Division FST-80 spectrometer.
2.4.2. Characterization of membranes
The membranes used for the chemical structure and mor-
phology analysis of the skin layer were rinsed with DI water for
several times. Then, the membranes were dried under vacuum
at 40 ◦ C for 24 h.
Attenuated total reflectance infrared (ATR-IR) characteriza-
tion of the TFC membrane surface was made with a Bio-Rad
digilab Division FST-80 spectrometer. For ATR-IR analysis of
membrane samples, Irtran crystal at 45◦ angle of incidence was
employed.
Surface chemical characterization was carried out by X-ray
photoelectron spectra (XPS), with a Thermo ESCALAB 280
system with Al/K (hν = 1486.6 eV) anode mono-X-ray source.
The contact angles of the active layer were estimated by Drop
Shape Analysis DSA10 (Krüˇ ss GmbH, Germany) at the ambient
temperature. Water droplets (about 5 mg) were dropped carefully
on to the layers.
Scanning electron microscopy (SEM) was performed with
XL 30 ESEM FEG, FEI Company. Magnifications up to 10,000
were obtained.
For atomic force microscope (AFM), measurements were
performed on SPA300HV with an SPI 3800 controller, Seiko
Instruments Industry Co. Ltd.
3. Results and discussion
3.1. Synthesis and characterization of monomers op-BTEC
and om-BTEC
The synthesis routes for the novel two isomeric compounds:
op-BTEC and om-BTEC are outlined in Scheme 1. Monomer
op-BTEC was synthesized from 1-bromo-2,5-dimethylbenzene
via Ni(0) catalytic coupling reaction, oxidation, and subsequent
chlorination. Monomer om-BTEC was synthesized from 1,3-
dimethyl-4-bromobenzene dicarboxylate via Ullmann coupling
reaction, hydrolysis, and subsequent chlorination reaction. The
chemical composition and structure of om-BTEC and op-BTEC
were confirmed by elemental analysis, FT-IR, 1 H NMR (Fig. 2).
3.2. Permeation properties of TFC RO membranes
In our previous study, the preparation parameters of the
interfacial polymerizations of the tetra-functional biphenyl acyl
chloride (I) with MPDA had been optimized. In present study,
TFC membranes op-BTRC/MPDA and om-BTRC/MPDA are
prepared using the same conditions. The PSf support layer
loaded with the aqueous solution of MPDA (2%, w/v) was
reacted with cyclohexane solution of the acyl chloride (0.1%,
w/v). The time of polymerization was 20 s. The RO rejection
and flux of the membranes was characterized at 2.0 MPa using
2000 ppm NaCl solution (pH 6.5) at 25 ◦ C in cross-flow cells.
The results of the performance test are shown in Fig. 3. It
can be seen from it that the membranes prepared from om-
BTEC and op-BTEC showed higher flux with the order of
op-BTEC > om-BTEC > mm-BTEC, but lower rejection with
the order of op-BTEC < om-BTEC < mm-BTEC compared with
membranes prepared from mm-BTEC. The reasons for differ-
ent permeation properties of those TFC membranes will be
discussed in the following section.
3.3. Characterization of the active layer
3.3.1. ATR-IR spectra and X-ray photoelectron
spectroscopy (XPS) analysis
The active layer of a TFC membrane is a very thin film that
bridges and overcoats the surface pores of the porous support.
The functional groups present in the barrier layer, after reaction
of the amine species with the cross-linking agent, could be iden-
tified by ATR-IR analysis of composite membrane samples. The
ATR-IR spectra of the active surface without the support layer
are shown in Fig. 4. It can be seen from Fig. 4 that no significant
differences could be observed among these spectra. For example,
 L. Li et al. / Journal of Membrane Science 315 (2008) 20–27 23

Scheme 1. Synthetic routes of op-BTEC and om-BTEC.

the spectrum of mm-BTEC/MPD displayed the characteristic
absorption bands of the amide appeared near 1657 (amide I),
1545 (amide II, C N stretch), and 1609 cm−1 (aromatic ring
breathing), which is identified as an evidence of formation of
functional NHCO bond. The peaks at 1729 cm−1 correspond
to the stretch of the C O in carboxylic acid groups formed by the
hydrolysis reaction of acyl chloride groups. The intensity ratio of
the band at 1657 cm−1 (amide I) and 1729 cm−1 (C O stretch
of carboxylic acid) for membranes prepared from mm-BTEC
was higher than the membranes from op-BTEC and om-BTEC.
This indicated that there were more carboxylic acid groups in
the active surface prepared from mm-BTEC than membranes
from other two isomeric acyl chloride monomers.
Monomers mm-BTEC, om-BTEC, and op-BTEC have the
same chemical compositions but different chemical structures.
The two acyl chloride groups are in the 2,2 -positions of biphenyl
unit for om-BTEC and op-BTEC but in the 3,3 -position of
biphenyl unit for mm-BTEC. This difference in the substitu-
tion position of the acyl chloride groups produces the different
monomer reactivities which should lead to different structural
properties of the polymers, including the degree of cross-linking
and chemical properties, such as hydrophilicity. These proper-

Fig. 2. 1 H NMR spectra of op-BTEC and om-BTEC.

24 L. Li et al. / Journal of Membrane Science 315 (2008) 20–27

Fig. 3. Comparison of permeation properties of the membranes.

Fig. 5. XPS spectra of the membrane surface.

of free carboxylic acid groups. The results measured from XPS

were consistent with that from ATR-IR.

3.3.2. Contact angle

Fig. 4. ATR-IR spectra of the active layer on the membranes.
ties affect not only the solubility but also the diffusivity of water
and salt.
The chemical composition of the ultra-thin polyamide on
the surface of the membrane was also analyzed by XPS. The
atomic composition (%) of the surface of the three membranes
determined by XPS was shown in Fig. 5 and Table 1. The
atomic ratio of O/N for the three membranes is in the order of
mm-BTEC > om-BTEC > op-BTEC. Since oxygen atoms exist
theoretically in the COOH and the functional NHCO bond
while nitrogen atoms in the NH2 groups and NHCO bond,
the higher O/N ratio for mm-BTEC implies the higher content
Table 1
XPS analysis of atomic concentrations and relative ratios of elements on the
membrane surface
Sample C (%) N (%) O (%) O/C N/C N/O
To study the hydrophilicity of the active thin film, we per-
formed contact-angle measurement with an image analyzer
system (Thermo ESCALAB 280 system). The contact angle is
a measure of the tendency for the water to wet the membrane
surface. The lower contact angle means the greater tendency
for water to wet the membrane and the higher hydrophilic-
ity. In these polyamides, the main components affecting the
hydrophilicity are an amide bond, an amine end group, and
a carboxylic acid end group. The amine end and carboxylic
acid group are more hydrophilic than the amide bonds of the
polyamide chain. The mm-BTEC/MPDA has a higher content of
free carboxylic acid groups, which result in a higher hydrophilic-
ity, as seen in Table 2.
Salt and water permeate reverse osmosis membranes accord-
ing to the solution-diffusion transport mechanism, so the
diffusivity of water is an important factor for the water flux. Reid
and Breton explained that the water permeation in RO mem-
branes by a hydrogen bond formation with functional groups of
membrane surface and a formation of bound water [22]. The
bound water passes through membrane from one hydrogen-
bonding site to another site in the membrane matrix under a
pressure gradient, and the passage of a solute component that
does not form a hydrogen bond is resisted. Both carboxylic acid
Table 2
Results of the measurement of contact angle
Sample 1 2 3 4 5 6 Average

mm-BTEC 71.32 9.31 19.37 0.272 0.131 0.481 mm-BTEC 76.2 78.3 77.6 74.5 71.8 77.3 76.0
om-BTEC 74.1 9.23 16.67 0.225 0.125 0.554 om-BTEC 84.7 79.3 81.2 78.8 84.5 82.3 81.8
op-BTEC 75.36 9.34 15.31 0.203 0.124 0.610 op-BTEC 78.2 81.3 84.2 81.8 80.6 79.6 81.0
 L. Li et al. / Journal of Membrane Science 315 (2008) 20–27 25

Fig. 6. SEM images: (a) top surface and cross-section of mm-BTEC; (b) top surface and cross-section of om-BTEC; (c) top surface and cross-section of op-BTEC.

group and amide functionality yield a short and strong H-bond with a projection area of 10 ␮m × 10 ␮m. As shown in Table 3,
with water. However, carboxylic acid groups form a slightly the order of the membrane roughness was op-BTEC > om-
more stable and strong H-bond with water than hydrophilic BTEC > mm-BTEC, and there was an obvious correlation of
amide groups. Higher stability of H-bond of carboxylic acid the water permeability with the surface roughness and surface
group with water would promise a more selective permeation area of the TFC membranes. It is obvious that the flux of the
but act as a resistance of the passage of the bound water from membrane increased in proportion to the increasing surface
one site to another [23]. In our case, mm-BTEC has lower water roughness and the enlarging surface area. The reason for the
flux than om-BTEC and op-BTEC. This may be contributed to its phenomenon might be that the rougher and larger surface area
higher carboxylic acid group content in the system. In addition, of the membranes made it possible to have contact with more
the molecular chain mobility and the morphology also affect the water molecules in the given projected area, which attributed the
permeation coefficient. higher flux.
The different morphologies of these TFC membranes may be
3.4. Morphology studies related to the different polymerization and diffusion rates of the
diamine monomer. The formation of the active layer prepared
In order to examine the effect of the acyl chloride structure from interfacial polymerization with amine monomer in aqueous
on morphology of membranes, the surface and cross-section of
the membranes were characterized by SEM. The SEM photos
Table 3
shown in Fig. 6 revealed that all the membranes had the similar Roughness and surface area of the membrane surface obtained from AFM
surface morphology, which was dense but not smooth. The white
part was the peak and the black part was the valley. The photos Sample Flux Rejection (%) Ra (nm) RMS (nm) S (␮m2 )
(l/(m2 h))
of the cross-section showed that the thickness of the active layer
was very thin, about 0.2 ␮m. mm-BTEC 31.7 98.4 147 186 613
As an important complementation of the SEM, AFM was om-BTEC 50.0 97.8 169 214 624
op-BTEC 54.2 97.2 196 252 677
also used to characterize surface morphology of the membranes.
Fig. 7 represented AFM surface images of the TFC membranes Ra : average roughness; RMS: root-mean-square roughness; S: surface area.
26 L. Li et al. / Journal of Membrane Science 315 (2008) 20–27
Fig. 7. AFM images: (a) the iamges of membranes prepared from mm-BTEC; (b) the iamges of membranes prepared from om-BTEC; (c) the iamges of membranes
prepared from op-BTEC.
phase and acyl chloride monomer in organic phase was con-
trolled by the amine monomer diffusion from aqueous phase into
organic phase. After the amine coming into the organic phase, it
reacted with the acyl chloride quickly and formed the polyamide
which would prevent the amine father diffusion. As described
previously, the polyamides prepared with mm-BTEC/MPDA,
op-BTEC/MPDA, and om-BTEC/MPDA have the same chem-
ical compositions but different chemical structures. There are
two acyl groups on the 2,2 -position of biphenyl groups for op-
BTEC and om-BTEC but in the 3,3 -positions of biphenyl groups
for mm-BTEC. Due to the steric hindrance for 2,2 -substituted
acyl chloride, the reactivity of om-BTEC and op-BTEC is
lower than that of mm-BTEC. For mm-BTEC/MPDA mem-
brane, the cross-linking degree should be higher than that of
TMC/MPDA membrane due to BTEC having four acyl groups
whereas TMC having three acyl groups. The high degree of
cross-linking may block the diffusion of the MPDA into the
organic phase, thus result a smooth morphology of mm-BTEC
membrane [18]. For op-BTEC/MPDA and om-BTEC/MPDA,
the low reactivity of 2,2 -substituted acyl chlorides leads to
the low degree of cross-linking, thus the high speed of amine
diffusion. This results in the increase of the roughness of the
membrane.
4. Conclusions
Three novel of isomeric tetra-functional biphenyl acid chlo-
ride: mm-BTEC, om-BTEC, and op-BTEC were synthesized,
and successfully used as new monomers for the preparations of
RO membranes through interfacial polymerization with MPDA.
The results of the performance testing showed that the mem-
branes prepared from om-BTEC and op-BTEC showed higher
flux with the order of op-BTEC > om-BTEC > mm-BTEC, but
lower rejection with the order of op-BTEC < om-BTEC < mm-
 L. Li et al. / Journal of Membrane Science 315 (2008) 20–27
BTEC compared with membranes prepared from mm-BTEC.
The results from ATR-IR and XPS showed that there were more
carboxylic acid groups on the membrane surface prepared from
mm-BTEC compared with membranes prepared from op-BTEC
and om-BTEC. The hydrophilicity of the membranes prepared
from mm-BTEC were better than membranes prepared from om-
BTEC and op-BTEC due to the higher content of carboxylic acid
on the active surface. However, the more stable and strong H-
bond of carboxylic acid group with water compared with amide
group acted as a resistance of the passage of the bound water
and resulted in the lower water flux for membranes prepared
from mm-BTEC compared with membranes prapared from om-
BTEC and op-BTEC. The reactivity of op-BTEC and om-BTEC
were lower than mm-BTEC due to the high-steric hindrance for
2,2 -substituted acyl chloride. The different chemical composi-
tion of the membrane surface, hydrophilicity and morphology
might come from the different reactivity and chemical structure
of the three acyl chloride monomers.
Acknowledgements
We thank the National Basic Research Program of China (no.
2003CB615704) and the National Science Foundation of China
(no. 20474061) for the financial support.
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