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Journal of Membrane Science 342 (2009) 300–306

Contents lists available at ScienceDirect

Journal of Membrane Science


journal homepage: www.elsevier.com/locate/memsci

Temperature- and pH-sensitive nylon membranes prepared via consecutive


surface-initiated atom transfer radical graft polymerizations
Z.B. Zhang a,b , X.L. Zhu b , F.J. Xu a,c , K.G. Neoh a , E.T. Kang a,∗
a
Department of Chemical and Biomolecular Engineering, National University of Singapore, Kent Ridge, Singapore 119260, Singapore
b
School of Chemistry & Chemical Engineering, Soochow University, Suzhou 215006, PR China
c
College of Materials Science & Engineering, Beijing University of Chemical Technology, Beijing 100029, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Thermo- and pH-responsive nylon membranes were prepared via consecutive surface-initiated
Received 7 February 2009 atom transfer radical polymerizations (ATRPs) of N-isopropylacrylamide (NIPAAm) and N,N -dimethyl
Received in revised form 24 June 2009 aminoethyl methacrylate (DMAEMA). The amide groups of the membrane and pore surfaces were first
Accepted 3 July 2009
activated for the immobilizing of alkyl halide ATRP initiator. The kinetics study revealed that the chain
Available online 14 July 2009
growth from the membranes was consistent with a “controlled” process. The dormant chain ends of the
grafted NIPAAm polymer (PNIPAAm) or DMAEMA polymer (PDMAEMA) on the nylon membranes could
Keywords:
be reactivated for the consecutive surface-initiated ATRP to produce the corresponding nylon membranes
Stimuli-responsive brushes
Nylon membrane
functionalized with PNIPAAm-b-PDMAEMA or PDMAEMA-b-PNIPAAm diblock copolymer brushes. The
ATRP permeation of aqueous solution through the functional membranes showed an abrupt change with tem-
PNIPAAm perature between 30 and 35 ◦ C, and pH between 6 and 8. The temperature- and pH-responsive permeation
PDMAEMA through the functional nylon membranes was found to be reversible and irrespective of the sequence of
the graft segments.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction membranes capable of responses to multiple environmental stimuli


are of both scientific and technological interest. The incorporation
Stimuli-responsive materials have been of great interests of desirable functionalities onto nylon surfaces can be accom-
because of their useful applications in various areas [1–6]. Stimuli- plished via several methods, such as plasma treatment [35,36], UV
responsive materials can be designed to sense and respond to irradiation [37,38], N-alkylation [25,39], potassium peroxydisulfate
various changes in environmental conditions, such as temperature oxidation [26,40], and surface-initiated atom transfer radical poly-
[7–10], pH [11,12], magnetic or electric fields [13–15], ionic strength, merization (ATRP) [41]. ATRP is a recently developed “living” or
and light [16,17]. The stimuli-responsive materials can be used in “controlled” radical polymerization method [42,43]. It is possible
the form of hydrogel [2], micelles [12], particles [18], and mem- to prepare well-defined polymer brushes on various substrates via
branes [19–22]. Among them, the stimuli-responsive membranes surface-initiated ATRP [44–47], provided that the ATRP initiators
have promising applications in areas, such as in controlled drug can be immobilized on the substrate surfaces a priori.
delivery, liquid mixture separation and water treatment, because In the present work, functional nylon membranes with thermo-
the flux or permeation through the membranes can be controlled and pH-sensitivity are designed and synthesized via consecutive
or triggered by external stimuli [20,21,23]. surface-initiated ATRP. Poly(N-isopropylacrylamide) (PNIPAAm)
Nylon membrane is one of the most versatile membranes and poly(N,N -dimethyl aminoethyl methacrylate) (PDMAEMA) are
because of its outstanding mechanical strength, flexibility, tough- selected as the functional polymer brushes, because they are well-
ness and abrasion resistance, as well as its good resistance to known, respectively, as the thermo- [22,48] and pH-responsive
solvents, oils, and biological fluids [24–26]. Nylon membranes [24,49] polymers. The covalent immobilization of ATRP initiators
are also widely used as matrices or substrates in biochemistry on the nylon membrane and its pore surfaces can be accomplished
and life sciences [27–29], separation and purification [30–33], and in a simple two-step process developed earlier (Scheme 1) [41].
hemodialysis [34]. However, more and more practical applications Functional polymer brushes of PNIPAAm and PDMAEMA, as well
require the use of functionalized nylon membranes. “Smart” nylon as their diblock copolymer brushes of different block lengths and
spatial block sequence, are then grafted from the membrane and
pore surfaces via surface-initiated ATRP (Scheme 1). The surface
∗ Corresponding author. Tel.: +65 6874 2189; fax: +65 6779 1936. composition and morphology of the modified nylon membranes
E-mail address: cheket@nus.edu.sg (E.T. Kang). are characterized by X-ray photoelectron spectroscopy (XPS) and

0376-7388/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2009.07.004
Z.B. Zhang et al. / Journal of Membrane Science 342 (2009) 300–306 301

Scheme 1. Diagram illustrating the activation of the amide groups of the nylon membrane by formaldehyde to produce the N-methylol-terminated Nylon-OH membrane,
reaction of the hydroxyl groups of the Nylon-OH membrane with 2-bromoisobutyrate bromide to produce the alkyl halide-terminated Nylon-Br membrane, and surface-
initiated ATRPs from the Nylon-Br membrane.

scanning electron microscopy (SEM), respectively. Temperature- per(I) bromide (CuBr, 99%), and copper(II) bromide (CuBr2 , >98%)
and pH-responses of the surface-functionalized nylon membrane were also obtained from Sigma–Aldrich Chemical Co.
are evaluated from the permeation rate of aqueous solutions as a
function of temperature and pH.
2.2. Immobilization of atom-transfer radical polymerization
(ATRP) initiators on the nylon membranes
2. Experimental
The immobilization of the ATRP initiators on the nylon mem-
2.1. Materials brane was carried out in two steps (Scheme 1): (1) activation
of the surface amide groups by formaldehyde to produce the
Nylon microfiltration membranes (GE nylon membrane, N-methylol polyamide membrane (Nylon-OH membrane) and
R12SP02500) with a diameter of about 25 mm and a thick- (2) reaction of the hydroxyl groups of the Nylon-OH mem-
ness of about 65 ␮m were obtained from GE Osmonics Lab- brane with 2-bromoisobutyryl bromide (BIBB) to produce the
store of Minnesota, MN. The membrane with an average 2-bromoisobutyryl-immobilized membrane (nylon-Br membrane)
pore size of about 5 ␮m was reinforced by polyester fibers. for the subsequent surface-initiated ATRP. Briefly, 50 mL of
The surface area (SA) and specific surface area (SSA) were formaldehyde solution and 1 mL of 85 wt% phosphoric acid were
about 4.9 cm2 and 4587 cm2 /g, respectively [41]. Formalde- introduced into a 100 mL flask containing 30 membrane discs. The
hyde (>36.5% w/w), 2-bromoisobutyryl bromide (BIBB, 98%), and reaction mixture was kept at 60 ◦ C for 12 h to produce the Nylon-
the monomers, N-isopropylacrylamide (NIPAAm, >99%) and 2- OH membranes. After the reaction, the Nylon-OH membranes were
(N,N -dimethylamino)ethyl methacrylate (DMAEMA, >98%), were washed and extracted exhaustively with copious amounts of water
obtained from Sigma–Aldrich Chemical Co. of Milwaukee, WI. The and then dried by pumping under reduced pressure. For the reac-
monomers were used after removal of the inhibitors in a ready- tion of hydroxyl groups of the Nylon-OH membrane with BIBB,
to-use disposable inhibitor-removal column (Sigma–Aldrich). 50 mL of chloroform and 4 mL of triethylamine were introduced into
1,1,4,7,10,10-Hexamethyl triethylene tetramine (HMTETA, 99%), a 100 mL flask containing 26 Nylon-OH membrane discs, followed
N,N,N ,N ,N -pentamethyldiethylenetriamine (PMDETA, 99%), cop- by the addition of 0.8 mL of BIBB. The reaction mixture was gently
302 Z.B. Zhang et al. / Journal of Membrane Science 342 (2009) 300–306

stirred for 5 min at 0 ◦ C and then for 15 min at room temperature to sitivity factor-corrected spectral area ratios and were reliable to
produce the Nylon-Br membranes. The Nylon-Br membranes were within ±5%. The surface morphologies of the membrane discs were
washed exhaustively with copious amounts of acetone and then imaged using a scanning electron microscope (JEOL SEM, model
with a methanol/water (1:1 v/v) mixture prior to being dried under 5600LV). Prior to the SEM measurements, the membranes were
reduced pressure. fixed on the metal holders and sputtered with a thin Pt layer.

2.3. Surface-initiated ATRP


3. Results and discussion
For surface-initiated ATRP of DMAEMA from the Nylon-Br
The immobilization of atom transfer radical polymerization
membranes, the reaction was carried out using a [DMAEMA
(ATRP) initiators on the nylon membrane is the precondition for
(1 mL)]:[CuBr]:[CuBr2 ]:[HMTETA] molar feed ratio of 100:1:0.4:1
the surface-initiated ATRP. A simple two-step method for the effec-
in 6 mL of a water–methanol mixture (H2 O:CH3 OH = 1:1 (v/v))
tive immobilization of ATRP initiators on the nylon membrane
at room temperature in a Pyrex tube containing five Nylon-
was developed earlier [41]. Initially, the amide groups on the
Br membrane discs. As for the graft polymerization of NIPAAm
nylon membrane and pore surfaces were activated by formalde-
from the Nylon-Br substrates, the reaction was carried out using
hyde to produce the N-methylol polyamide membrane (Nylon-OH).
a [NIPAAm (1 g)]:[CuBr]:[CuBr2 ]:[PMDETA] molar feed ratio of
Then, the hydroxyl groups on the Nylon-OH membrane were
100:1:0.2:1 in 6 mL of deionized water at room temperature
reacted with 2-bromoisobutyryl bromide (BIBB) to produce the
in a Pyrex tube containing five Nylon-Br membrane discs. The
alkyl halide-functionalized nylon membrane (Nylon-Br). The sur-
graft polymerization was allowed to proceed for a predeter-
face and internal morphologies of the nylon membrane remain
mined period of time. The resulting nylon membranes with
practically unchanged after the modification and immobilization
surface-grafted DMAEMA polymer (PDMAEMA) and NIPAAm poly-
of the ATRP initiators [41]. The subsequent surface-initiated ATRP
mer (PNIPAAm) are referred to as the Nylon-g-PDMAEMA and
was carried out from the Nylon-Br membrane. Results of the surface
Nylon-g-PNIPAAm membranes, respectively. The resulting Nylon-
functionalization processes are discussed below.
g-PDMAEMA and Nylon-g-PNIPAAm membranes were washed
and extracted thoroughly with ethanol and then doubly dis-
tilled water. The membranes were immersed subsequently in a 3.1. Surface-initiated ATRP from the Nylon-Br membrane
large volume of ethanol for about 48 h to ensure the complete
removal of the adhered and physically adsorbed reactants, prior In this work, (2-dimethyl amino)ethyl methacrylate (DMAEMA)
to being dried under reduced pressure. The monomer conver- and N-isopropylacrylamide (NIPAAm) were selected as the
sion was determined gravimetrically according to the equation: model monomers for the preparation of functional polymer
conversion (%) = (Wa − Wb )/Wm , where Wa and Wb represent the brushes from the Nylon-Br membranes via surface-initiated ATRP.
weights of the dry membrane after and before graft polymeriza- Poly(N-isopropylacrylamide) (PNIPAAm) is a well-known thermo-
tion, respectively, and Wm is the weight of the monomer added. responsive polymer, which exhibits a lower critical solution
The dormant alkyl halide end groups of the grafted chains can temperature (LCST) of about 32 ◦ C in an aqueous medium. The
be used as the macro-ATRP initiators for the subsequent block reversible phase transition of PNIPAAm has been widely used in the
copolymerization. Nylon-g-PDMAEMA-b-PNIPAAm and Nylon-g- synthesis of thermo-responsive materials. Poly[2-(N,N -dimethyl
PNIPAAm-b-PDMAEMA membrane were prepared by reactivating aminoethyl methacrylate)] (PDMAEMA) is a pH-sensitive polymer
the dormant chain ends on the corresponding Nylon-g-PDMAEMA arising from the pendant amine groups. The nylon membrane with
and Nylon-g-PNIPAAm membranes. The second round of surface- its surface (including the pore surfaces) grafted with PDMAEMA
initiated ATRP was carried out under the same reaction conditions and PNIPAAm is expected to be sensitive to changes in both tem-
as those described above for the preparation of the initial block. perature and pH, and may have practical uses in stimuli-responsive
and controlled permeation. CuBr2 acting as the deactivator in the
2.4. Measurements of the temperature- and pH-dependent flux ATRP process was added to the polymerization system in order to
through the graft-modified nylon membranes maintain a well-controlled surface-initiated ATRP from the early
stage of the polymerization [25,47].
The flux of aqueous solutions through the membranes was car- The presence of grafted PNIPAAm and PDMAEMA brushes on
ried out under an argon pressure of 0.2 kg/cm2 . The pristine nylon the Nylon-Br membranes was confirmed by XPS analysis after the
membrane, the Nylon-g-PDMAEMA-b-PNIPAAm membrane, or the surfaces had been subjected to vigorous washing and extraction.
Nylon-g-PNIPAAm-b-PDMAEMA membrane was mounted on the Fig. 1 shows the respective wide-scan and C 1s core-level spectra of
microfiltration cell (Toyo Roshi UHP-25, Tokyo, Japan) which was Nylon-g-PDMAEMA2, Nylon-g-PNIPAAm2, Nylon-g-PDMAEMA2-
immersed in a thermostated water bath (LAUDA, Nr. U16005, Ger- b-PNIPAAm and Nylon-g-PNIPAAm2-b-PDMAEMA membranes.
many) at a predetermined temperature. An aqueous solution of The conditions for the surface functionalization of the respective
prescribed pH value was introduced into the microfiltration cell, membranes are given in Table 1. The C 1s core-level spectrum
which was equilibrated in the thermostated water bath for 30 min of the Nylon-g-PDMAEMA2 membrane surface (Fig. 1b) can be
prior to the initiation of the flux. The flux was calculated from the curve-fitted into four peak components with BEs at about 284.6,
permeate volume as a function of time. The pH value of the solution 285.7, 286.2, and 288.7 eV, attributable to the C–H, C–N, C–O and
was determined by a Mettler Toledo Delta 320 pH meter. O C–O species, respectively [50]. The O C–N species at the BE of
287.4 eV from the pristine nylon membrane [41] has disappeared
2.5. Membrane characterization completely. The [C–N]:[C–O]:[O C–O] peak component area ratio
of about 3.1:1.0:1.1 is in fairly good agreement with the theoretical
The surface chemical composition and morphology of the mod- molar ratio of 3:1:1 for the PDMAEMA homopolymer. These XPS
ified nylon membranes were characterized by X-ray photoelectron results indicate that the membrane surface has been completely
spectroscopy (XPS) and scanning electron microscopy (SEM). XPS covered by the PDMAEMA brushes to a thickness exceeding the
measurements were performed on a Kratos AXIS HSi spectrometer sampling depth of the XPS technique (about 7.5 nm in an organic
using a monochromatized Al K␣ X-ray source (1486.6 eV photons). matrix [51]). Fig. 1c and d shows the respective wide scan and C 1s
Surface elemental stoichiometries were determined from the sen- core-level spectra of the Nylon-g-PNIPAAm2 membrane. The C 1s
Z.B. Zhang et al. / Journal of Membrane Science 342 (2009) 300–306 303

spectrum of the Nylon-g-PDMAEMA2-b-PNIPAAm (Fig. 1f) can be


curve-fitted into four peak components with BEs at about 284.6,
285.7, 286.2, and 288.7 eV, attributable to the C–H, C–N, C–O and
O C–O species, respectively. The peak components at the BEs of
about 285.7 and 287.4 eV can be attributed, respectively, to the C–N
and O C–N species associated with PNIPAAm. The C 1s peak com-
ponents at the BEs of 286.2 and 288.7 eV, associated with the C–O
and O C–O species from the underlying PDMAEMA segment have
disappeared almost completely. With the alkyl halide on the Nylon-
g-PNIPAAm2 membrane as the macro-initiator for the consecutive
ATRP of DMAEMA, the corresponding C 1s core-level spectrum of
the Nylon-g-PNIPAAm2-b-PDMAEMA membrane (Fig. 1h) can be
curve-fitted into five peak components with BEs at about 284.6,
285.7, 286.2, 287.4 and 288.7 eV, attributable to the C–H, C–N, C–O,
O C–N and O C–O species, respectively. Two new peak compo-
nents (compared to those of Nylon-g-PNIPAAm2 surface of Fig. 1d)
at the BEs of 286.2 and 288.7 eV, attributable to the C–O and O C–O
species, respectively, of the grafted DMAEMA polymer chains have
appeared. Thus, the block copolymerization results have confirmed
that the dormant alkyl halide groups at the grafted PDMAEMA and
PNIPAAm chain ends have allowed reactivation during the subse-
quent surface-initiated block copolymerization process, resulting
in the formation of diblock copolymer brushes on the nylon mem-
branes.

3.2. Morphology of the surface-functionalized membranes

Fig. 2 shows the respective SEM images (top views) of the


(a) pristine nylon, (b) Nylon-Br, (c) Nylon-g-PDMAEMA2, (d)
Nylon-g-PNIPAAM2, (e) Nylon-g-PDMAEMA2-b-PNIPAAm and (f)
Nylon-g-PNIPAAm2-b-PDMAEMA membranes. After the graft poly-
merization, the membrane surface became densely covered by
polymer chains, and the effective dimension of pore channels was
Fig. 1. Wide-scan and C 1s core-level spectra of the Nylon-g-P(PDMAEMA)2, reduced from that of the starting nylon (Fig. 2a) and Nylon-Br
Nylon-g-PNIPAAM2, Nylon-g-P(PDMAEMA)2-b-PNIPAAm and Nylon-g-PNIPAAM2- (Fig. 2b) membranes. Thus, the SEM results are consistent with
b-PDMAEMA membrane surfaces. (The preparation conditions for the membranes
are given in Table 1).
the presence of grafted homopolymers and block copolymers of
DMAEMA and NIPAAm.
The kinetics of graft polymerizations of DMAEMA and NIPAAm
core-level spectrum of the Nylon-g-PNIPAAm2 membrane surface from nylon membranes via surface-initiated ATRP was investigated.
(Fig. 1d) can be curve-fitted into three peak components with BEs The results are shown in Fig. 3. DMAEMA and NIPAAm can be read-
at about 284.6, 285.7 and 287.4 eV, attributable to the C–H, C–N and ily graft polymerized by ATRP from the modified nylon membrane
O C–N species, respectively [50]. The [C–H]:[C–N]:[O C–N] peak (Nylon-Br) at room temperature. Furthermore, an approximate lin-
component ratio of about 4.2:0.9:1.0 is in good agreement with ear increase in ln([M]0 /[M]), where [M]0 and [M] were the initial and
the theoretical molar ratio of 4:1:1 for the PNIPAAm homopolymer, instantaneous monomer concentrations, respectively, with poly-
indicating that the membrane surface has been completely covered merization time was observed. These results suggested that the
by the PNIPAAm brushes. chain growth of PDMAEMA and PNIPAAm from the Nylon-Br mem-
The dormant alkyl halide groups of Nylon-g-PDMAEMA2 can be branes via surface-initiated ATRP was well-controlled [43]. The
reactivated for the preparation of diblock copolymer brushes in the graft yield based on the membrane surface area (SA), denoted as
subsequent surface-initiated ATRP of NIPAAm. The C 1s core-level GYSA , and on the specific surface area (SSA), denoted as GYSSA , can

Table 1
Reaction conditions and graft yield (GY) of the graft-modified nylon membranes from surface-initiated ATRP.

Samplea Reaction time (min) Graft yield (GY)b

GYSA (mg/cm2 ) GYSSA (␮g/cm2 )

Nylon-g-PDMAEMA1 15 6.0 6.4


Nylon-g-PDMAEMA2 30 9.1 9.7
Nylon-g-PNIPAAm1 5 6.1 6.5
Nylon-g-PNIPAAm2 10 16.4 17.5
Nylon-g-PDMAEMA2-b-PNIPAAmc 10 9.1 + 15.7 9.7 + 16.8
Nylon-g-PNIPAAm2-b-PDMAEMAc 45 16.4 + 12.9 17.5 + 13.8
a
Reaction conditions: DMAEMA as monomer – [DMAEMA (1 mL)]:[CuBr]:[CuBr2 ]:[HMTETA] molar feed ratio = 100:1:0.4:1 in 6 mL of a water–methanol mixture
(H2 O:CH3 OH = 1:1 (v/v)) at room temperature; NIPAAm as the monomer – [NIPAAm (1 g)]:[CuBr]:[CuBr2 ]:[PMDETA] molar feed ratio = 100:1:0.2:1 in 6 mL of deionized
water at room temperature.
b
Graft yield (GY) is defined as GYSA (or GYSSA ) = (Wa − Wb )/SA (or (Wa − Wb )/SSA), where Wa and Wb represent the weights of the dry membrane after and before grafting,
respectively, and SA and SSA are the respective surface area and specific surface area of the membrane.
c
Surface-initiated ATRP from the corresponding Nylon-g-PDMAEMA2 or Nylon-g-PNIPAAm2 membrane surfaces.
304 Z.B. Zhang et al. / Journal of Membrane Science 342 (2009) 300–306

Fig. 2. SEM images (top view) of the (a) pristine nylon, (b) Nylon-Br, (c) Nylon-g-PDMAEMA2, (d) Nylon-g-PNIPAAm2, (e) Nylon-g-PDMAEMA2-b-PNIPAAm and (f) Nylon-g-
PNIPAAm2-b-(DMAEMA) membranes. (The preparation conditions for the membranes are given in Table 1).

be evaluated (Table 1). GYSA and GYSSA were calculated according 3.3. Thermo- and pH-responsive flux of aqueous medium through
to the equations: GYSA = (Wa − Wb )/SA and GYSSA = (Wa − Wb )/SSA, the membranes
respectively. The GYSA and GYSSA values are about 9.1 mg/cm2 and
9.7 ␮g/cm2 for the Nylon-g-PDMAEMA2 membrane, respectively, Since the pore channels of the nylon membrane have been
and about 16.4 mg/cm2 and 17.5 ␮g/cm2 for the Nylon-g-PNIPAAm2 successfully grafted with the PNIPAAm and PDMAEMA block
membrane. Furthermore, grafted block copolymers, PDMAEMA-b- copolymers via consecutive surface-initiated ATRP, the flux through
PNIPAAm and PNIPAAm-b-PDMAEMA, were also obtained using the membrane is expected to show responses to changes in tem-
the respective Nylon-g-PDMAEMA and Nylon-g-PNIPAAm mem- perature and pH of the medium or environment. The flux of
brane surface as the macro-ATRP initiators. The respective GYSSA aqueous solutions through the Nylon-g-PDMAEMA2-b-PNIPAAm
values confirm with that the pore surfaces of the nylon membranes and Nylon-g-PNIPAAm2-b-PDMAEMA membranes was investi-
have also been densely grafted with homo- and block copolymers gated as functions of both temperature (in the temperature range
(Table 1). of 25–45 ◦ C at pH = 7.0) and pH (in the pH range of 4.8–12 at
25 and 35 ◦ C) of the permeate. The results are summarized in
Figs. 4 and 5, respectively. In Fig. 4, the flux of the aqueous
solution through the membranes was almost unchanged when
the temperature was below 30 ◦ C. A dramatic increase in per-
meation rate was observed at temperatures between 30 and
35 ◦ C. When the permeate temperature was increased to 35 ◦ C,
the flux again exhibited a weak dependence on temperature. The
flux at 40 ◦ C was about 2.4 times that at 20 ◦ C for the Nylon-g-
PNIPAAm2-b-PDMAEMA membrane (Fig. 4a), and 2.7 times for
the Nylon-g-PDMAEMA2-b-PNIPAAm membrane (Fig. 4b). The
similarity in temperature-dependent flux behavior for the Nylon-
g-PNIPAAm2-b-PDMAEMA and Nylon-g-PDMAEMA2-b-PNIPAAm
membranes indicate that the temperature-response is independent
of the sequence of the stimuli-responsive block in the diblock poly-
mer chain. In a control experiment using pristine nylon membranes,
no obvious dependence of flux on permeate temperature was
found. The flux through the pristine nylon membrane was about
3.1 mL/(min cm2 ) in the temperature range of 25–45 ◦ C, which
was about 55 times that of the Nylon-g-PNIPAAm2-b-PDMAEMA
membrane (Fig. 4a) at 25 ◦ C. All these results indicate that the
Fig. 3. Kinetics of graft polymerization of DMAEMA and NIPAAm from the surface
of nylon membrane via surface-initiated ATRP. ([M]0 and [M] are the initial and
thermo-responsive properties of the graft-modified nylon mem-
instantaneous monomer concentrations, respectively). branes are regulated by the PNIPAAm segments. The lower critical
Z.B. Zhang et al. / Journal of Membrane Science 342 (2009) 300–306 305

Fig. 4. Temperature-dependent permeability of aqueous solutions in the tempera- Fig. 5. pH-dependent permeability of aqueous solutions through the Nylon-
ture range of 25–45 ◦ C through (a) the Nylon-g-PNIPAAm2-b-PDMAEMA and pristine g-PDMAEMA2-b-PNIPAAM and Nylon-g-PNIPAAm2-b-PDMAEMA membranes at
nylon membrane, and (b) the Nylon-g-PDMAEMA2-b-PNIPAAM membrane. The pH temperatures of (a) 25 ◦ C, and (b) 35 ◦ C. The imposed pressure for flow was
of the solution was 7.0 and the imposed pressure for flow was 0.2 kg/cm2 . 0.2 kg/cm2 . The thickness of the pristine nylon membranes was about 65 ␮m,
while the thicknesses of Nylon-g-PDMAEMA2-b-PNIPAAM and Nylon-g-PNIPAAm2-
b-PDMAEMA membranes were about 80 and 85 ␮m, respectively.

solution temperature (LCST) of the NIPAAM polymer is about 32 ◦ C.


At a permeate temperature below the LCST, the grafted PNIPAAM increases as a result of the increase in effective pore size. For the
segments are hydrophilic and assume an extended (hydrated) Nylon-g-PDMAEMA2-b-PNIPAAm membrane, the flux at pH = 12
conformation on the membrane and pore surfaces, reducing the and temperature = 35 ◦ C was 0.24 mL/(min cm2 ), which was 2.5
effective pore size and thus, the permeation rate of the aqueous times that at pH = 4.8 (Fig. 5b). Similar pH-dependent results were
solution. At permeate temperatures above the LCST, the PNIPAAm obtained for the Nylon-g-PNIPAAm2-b-PDMAEMA membrane. The
chains associate hydrophobically on the membrane and pore sur- sequence of the polymer chains again does not exert a significant
faces, resulting in the opening up of pores in the membrane and effect on the pH-response of the graft-modified membranes.
hence the observed increase in flow rate. Meanwhile, when the
temperature was lowed from 45 to 25 ◦ C, the flux also showed 4. Conclusions
an abrupt decrease between 35 and 30 ◦ C, indicating that the
temperature-response was completely reversible. Again, the Nylon- Nylon membrane and its pore surfaces were successfully
g-PDMAEMA2-b-PNIPAAm and Nylon-g-PNIPAAm2-b-PDMAEMA functionalized via consecutive atom transfer radical graft poly-
membranes showed the same temperature responses, regardless merization of DMAEMA and NIPAAm. Kinetics studies revealed
of the block sequence, in repeated temperature cycling. the features of “living”/controlled radical polymerization. XPS
The flow rate of aqueous solution through the Nylon- and SEM results confirmed the successfully grafting of the
g-PNIPAAm2-b-PDMAEMA and Nylon-g-PDMAEMA2-b-PNIPAAm stimuli-responsive polymers and block copolymers from the nylon
membranes was also measured as a function of permeate pH at membranes. The flux of aqueous solution through the surface-
a constant temperature of 25 ◦ C (Fig. 5a) and 35 ◦ C (Fig. 5b). At functionalized nylon membranes exhibited a transition in the
both temperatures, the flux exhibits a marked increase when pH temperature range between 30 and 35 ◦ C, and in the pH range
of the medium is increased from 6 to 8. The flux through pris- between 6 and 8. The sequence of PNIPAAm and PDMAEMA blocks
tine nylon membrane (Fig. 5a) does not exhibit any dependence in the grafted copolymer brushes did not have an obvious effect
on the pH of permeate. The pH-sensitive flux through the surface- on the observed thermo- and pH-response of the membranes. The
functionalized nylon membranes can be attributed to the presence functionalized nylon membranes are thus “smart” membranes suit-
of PDMAEMA segments on the grafted nylon membrane. PDMAEMA able for applications in water treatment, aqueous separation and
has amine pendant groups. Under acidic conditions (pH < 6.0), controlled flux of aqueous media.
the amine groups are partially protonated and assume a more
extended conformation, resulting in a decrease in effective pore
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