SEPARATION SCIENCE AND ENGINEERING

Chinese Journal of Chemical Engineering, 19(2) 262ü266 (2011)

Preparation of Thin Film Composite Nanofiltration Membrane by

Interfacial Polymerization with 3,5-Diaminobenzoylpiperazine and
Trimesoyl Chloride*

WANG Lihong (⧁ѳ㓘)1, LI Deling (ᶄᗭ⧨)1, CHENG Lihua (ぁѳ঄)2,3, ZHANG Lin (ᕖ᷍)2,3,**
and CHEN Huanlin (䱾⅘᷍)2,3
1
Department of Chemistry, Tangshan Normal College, Tangshan 063000, China
2
Department of Chemical & Biological Engineering, Zhejiang University, Hangzhou 310027, China
3
The Engineering Central of Membrane and Water Treatment, MOE, Hangzhou 310027, China

Abstract A new aromatic diamine, 3,5-diaminobenzoylpiperazine (3,5-DABP), was synthesized from 3,5-diaminobenzoic
acid and 1-formyl piperazine. The structure of 3,5-DABP was identified by FT-IR spectra and 1H NMR spectra.
With 3,5-DABP as aqueous monomer and trimesoyl chloride (TMC) as organic monomer, thin film composite (TFC)
nanofiltration membranes were prepared by interfacial polymerization technology. The salt rejection order of these
TFC membranes is Na2SO4>MgSO4>MgCl2>NaCl. This sequence indicates that the membranes are negatively charged.
Keywords thin film composite membrane, 3,5-diaminobenzoylpiperazine, trimesoyl chloride, interfacial polymerization

1 INTRODUCTION
Thin film composite (TFC) membranes for nano-
filtration (NF) have received tremendous attention
over last two decades in desalination of brackish and
sea water, waste water reclamation, ultrapure water
production, etc. Among the methods for preparing
TFC membranes, interfacial polymerization (IP) is the
most effective one. In an IP process for TFC mem-
brane, two reactive monomers are dissolved in immis-
cible aqueous and organic phases separately, and the
polymerization reaction takes place at the interface
between two phases, which is generally the surface of
the porous support membrane. Polyamide TFC mem-
branes are currently the most widely used nanofiltra-
tion membranes [1, 2]. The monomers in the aqueous
phase include different aliphatic or aromatic diamine
[37]. The monomers used in the organic phase are
usually a series of aromatic acyl chlorides [8, 9]. New
monomers are needed to develop membranes with
sufficient salt rejection and excellent flux.
In this work, a new aromatic diamine
3,5-diaminobenzoylpiperazine (3,5-DABP) is synthe-
sized. It has been reported in Tomaschke’s patent [10],
but the process is long and complicated. In order to
simplify the operation and increase the yield, we pro-
pose a simple method. With 3,5-DABP as aqueous
monomer and TMC as organic monomer, a thin film is
formed on the substrate membrane by IP technology.
The performance of the prepared composite mem-
brane is investigated.
2 EXPERIMENTAL
2.1 Materials
3,5-Diaminobenzoic acid (98%), 1-formyl piperazine
(98%), and trimesoyl chloride (TMC) from J&K
Chemical Ltd., were used as received. All the other
chemicals were of analytical grade and used without
further purification.
Polyethersulfone (PES) ultrafiltration (UF) mem-
brane, served as substrate membrane, was prepared
according to traditional phase inversion method. The
molecular mass cut-off was about 67000 (67 kDa).
2.2 Synthesis of 3,5-DABP
In a 250 ml three-necked round-bottom flask
equipped with magnetic stirring, 3,5-diaminobenzoic
acid (15.2 g, 0.1 mol) and formic acid (150 ml) were
added. The mixture was refluxed with stirring at 100 °C
for 12 h to produce the diformyl-protected compound.
After removal of formic acid by filtration, the solid
was washed with excess water and dried. The yield
was 97%.
The diformyl-protected compound (10.4 g, 0.05
mol) was dissolved in N,N-dimethylformamide (DMF)/
tetrahydrofuranate (THF) solvent (125 ml, volume ratio
of 1Ή4). 1-formyl piperazine (5.7 g, 0.05 mol) was
introduced and reacted with the diformyl-protected
compound at 60 °C for 24 h. The resulting solution
was first cooled to room temperature and then crystal-
lized in a refrigerator for 6 h. The crystallization was
collected through filtration and purified through
washing with THF. The white solid was dried to give

Received 2010-04-27, accepted 2010-11-18.

* Supported by the National Natural Science Foundation of China (21076176), the Research and Development Project of Tang-
shan (10140201C-3), the Research and Development Project of Hebei Province (07275113), and the Research Fund of Tang-
shan Normal College.
** To whom correspondence should be addressed. E-mail: linzhang@zju.edu.cn
 Chin. J. Chem. Eng., Vol. 19, No. 2, April 2011
the triformyl-protected compound. The yield was 72%.
Deformylation of the triformyl-protected com-
pound (10 g, 0.03 mol) was carried out at room tem-
perature in the mixture solvent (150 ml) of methanol
and hydrochloric acid (volume ratio of 4Ή1) for 2 h.
After evaporation, the solid residue was washed with
THF and dried as 3,5-DABP hydrochloride salt. This
compound was dissolved in ice water and adjusted to
pH 10 using strong base ion exchange resin. After
suction filtering and washing the resin with water, the
filtrate was evaporated azeotropically with anhydrous
ethanol, providing 3,5-DABP product as a fine white
powder. The yield was 70%.
2.3 Fabrication of the composite NF membrane
by IP
The composite NF membrane was prepared by
forming a skin layer over the microporous PES UF
membrane through the in situ IP technique. First, the
aqueous phase solution was prepared by dissolving a
certain amount of 3,5-DABP and dodecyl sulfonic
acid sodium salt (DDS) (0.05%) in water. The organic
phase solution was prepared with a certain amount of
TMC and hexane. Then, the PES UF membrane was
soaked in the aqueous phase solution for 15 min. Ex-
cess solution was drained from the surface and air-dried
at room temperature until no liquid left. The substrate
membrane was immersed in the organic phase solu-
tion for 2 min. After removing the excess solution, the
membrane was heated in an oven for further polym-
erization. Finally, the membrane was rinsed with de-
ionized water and stored in it for performance testing.
2.4 Characterization
2.4.1 Characterization of 3,5-DABP
The 1H NMR spectrum was measured at 500 MHz
on an AVANCE DMX-500 spectrometer. The FT-IR
spectrum was obtained with a Tensor37 spectrometer
(Bruker, Germany).
2.4.2 Morphologies of the composite NF membrane
The morphology of the composite NF membrane
was observed with scanning electron microscopy
(SEM), performed with KYKY-2800B, KYKY Tech-
nology Development Ltd., China.
2.5 Membrane performance evaluation
The composite nanofiltration membranes were
evaluated for salt flux and salt rejection on a nanofil-
tration test kit (Fig. 1). The effective membrane area
for each cell was 17.3 cm2.
The membrane was stabilized at 0.5 MPa for at
least 30 min with deionized water before testing. Then
NaCl, Na2SO4, MgCl2 and MgSO4 salt solutions of
1.5 g·L1 flowed across the membrane under a pres-
263
Figure 1 Schematic representation of the nanofiltration
evaluation kit
1üfeed tank; 2üfeed pump; 3ümembrane cell; 4üvalve;
5üpressure gauge
sure of 0.4 MPa at ambient temperature separately.
After the completion of each experiment or before
changing the feed, the membrane was rinsed with de-
ionized water until the conductivity of water was be-
low 10 ȝs·cm1.
The flux, F, is calculated as follows
V
F (1)
At
where V is the total volume of the solution permeated,
A is the effective membrane area, and t is the opera-
tion time. The salt rejection, R, is
§ Cp ·
R ¨1  ¸ u 100% (2)
© Cf ¹
where Cp and Cf are the salt concentrations in the
permeate and feed, respectively. Salt concentration was
determined by measuring the conductivity of the solu-
tion using a conductance meter (DDS-11A, Shanghai
Leichi Instrument, China).
All membrane samples were prepared and tested
at least twice with 3 membranes for NF performance,
and the average values are reported.
3 RESULTS AND DISCUSSION
3.1 Synthesis and characterization of 3,5-DABP
The synthetic route of 3,5-DABP was outlined in
Fig. 2. Compared with the route in Tomaschke’s pat-
ent [10] as shown in Fig. 3, this route is much simpler.
The step to form an intermediate using 1,1ƍ-carbonyl
diimidazole is omitted.
The chemical structure of the product was identi-
fied by FT-IR and 1H NMR. As shown by FT-IR spec-
trum in Fig. 4, 1664 cm1 is the characteristic peak
representing the formation of functional NCO .
3209 cm1, 3330 cm1 and 3396 cm1 are the charac-
teristic peaks of N H. The 1H NMR spectrum of
3,5-DABP is shown in Fig. 5, depicting the structure
and the corresponding peaks. From Figs. 4 and 5 it is
concluded that OH group in 3,5-diaminobenzoic
acid is substituted by piperazine group.
264 Chin. J. Chem. Eng., Vol. 19, No. 2, April 2011

Figure 2 Synthetic route for 3,5-DABP

Figure 3 Synthetic route for 3,5-DABP in Tomaschke’s patent [10]

3.2 Morphology of the composite NF membrane

Figure 6 shows the morphology of surface and

cross-section of the composite NF membrane. Since
the pore size on the skin layer is usually in the magni-
tude of nanometers, it is unable to observe the pore
structure at the surface [Fig. 6 (a)]. The cross-section
image [Fig. 6 (b)] shows a thin layer covering the
substrate membrane with regular finger-like pores. It
indicates that a skin layer is formed on the micropor-
ous substrate membrane by IP.
Figure 4 FT-IR spectrum of 3,5-DABP
3.3 Variation of membrane performance with
reactant concentrations

The salt flux and salt rejection of the composite

membranes prepared with different concentrations of
3,5-DABP and TMC are shown in Figs. 7 and 8, respec-
tively. The flux decreases as the reactant concentration
increases. The salt rejection first increases as reactant
concentration increases and then level off. The opti-
mum concentrations of 3,5-DABP and TMC are
1%2% (by mass) and 0.5% (by mass), respectively.
The variation of salt flux and salt rejection with
reactant concentrations may be owing to the chemical and
morphological changes during the formation of poly-
1
Figure 5 H NMR spectrum of 3,5-DABP amide skin layer. Just as the interfacial polymerization
 Chin. J. Chem. Eng., Vol. 19, No. 2, April 2011
(a) Surface scan
(b) Cross-section
Figure 6 SEM of the composite membrane
(a) Salt flux
(b) Salt rejection
Figure 7 Variation of membrane performance with
3,5-DABP concentration (TMC 0.25%, curing temperature
70 °C, curing time 15 min)
ƽ NaCl;ͩMgCl2;ƷMgSO4;ƾNa2SO4
between diamine and acid chloride [11], the interfacial
polymerization between 3,5-DABP and TMC occurs
on the organic side of the aqueous-organic interface.
The reaction is mainly controlled by the diffusion of
265
(a) Salt flux
(b) Salt rejection
Figure 8 Variation of membrane performance with TMC
concentration (3,5-DABP 1.5%, curing temperature 70 °C,
curing time 15 min)
ƽ NaCl;ͩMgCl2;ƷMgSO4;ƾNa2SO4
3,5-DABP through the polyamide film formed at the
interface and the diffusion of TMC in the organic
phase. At low concentrations of monomers, the rate of
polymerization is expected to be low due to the insuf-
ficient monomers at the interfacial polymerization site,
resulting in the formation of “thin and loose” polyam-
ide skin layer. The permeation rate of salts is high and
the desalination is low. With the increase of monomers,
thicker and more compact polyamide network forms
due to higher monomer concentrations and higher rate
of polymerization. The salt rejection increases and the
flux decreases. However, when monomer concentra-
tions increase to a certain value the polymerization
rate increases rapidly. The thick and compact film
formed prevents the diffusion of monomers through
the interface and the polymerization reaction stops.
The polymerization rate attains the maximum value.
There is little effect on the membrane performance at
higher monomer concentrations. Therefore, there may
exist optimum concentrations of reactants to obtain a
membrane with the best performance.
3.4 Rejection for different salts of the composite
NF membranes
Figures 7 and 8 also show the rejection and their
fluxes of the membranes for different salts. The salt
rejection order is Na2SO4>MgSO4>MgCl2>NaCl. This
266 Chin. J. Chem. Eng., Vol. 19, No. 2, April 2011
demonstrates that the composite membranes prepared
are negatively charged. This order can be explained by
Donnan exclusion. A negatively charged NF mem-
brane presents higher rejection to high-valence anions
than to low-valence anions.
4 CONCLUSIONS
A novel monomer, 3,5-DABP, was synthesized suc-
cessfully using a new method. The method is simple and
easy to carry out. FT-IR spectrum and 1H NMR spectrum
proves that the OH group in 3,5-diaminobenzoic
acid is substituted by piperazine group.
Composite nanofiltration membranes were pre-
pared by IP technology with 3,5-DABP as the aqueous
monomer and trimesoyl chloride as the organic
monomer. SEM images of the membrane show that a
skin layer is fabricated on the porous polyethersulfone
ultrafiltration membrane. The salt flux and salt rejec-
tion of the composite membrane varies with mono-
mers concentrations.
The rejection for different salts and their salt flux
were compared. The salt rejection order is Na2SO4>
MgSO4>MgCl2>NaCl. Thus the resultant membranes
are all negatively charged nanofiltration membranes.
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