Macromolecules 2007, 40, 2271-2275 2271

Conductive Hollow Nanospheres of Polyaniline via (void dimension and shell thickness) and uniform size. Fur-
Surface-Initiated Atom Transfer Radical thermore, the so-obtained hollow nanospheres are expected to
Polymerization of 4-Vinylaniline and Oxidative have good structural integrity because of chain entanglements
in the dense comb-shaped P(VAn-g-PANI) brushes which
Graft Copolymerization of Aniline
constitute the shell.
G. D. Fu,*,† J. P. Zhao,‡ Y. M. Sun,† E. T. Kang,*,‡ 2. Results and Discussion
and K. G. Neoh‡
The atom transfer radical polymerization (ATRP) initiator,
School of Chemistry & Chemical Engineering, Southeast
UniVersity, Nanjing, P. R. China 210096, and Department of trichloro(4-chloromethylphenyl)silane, was immobilized on the
Chemical & Biomolecular Engineering, National UniVersity silica nanoparticles of about 25 nm diameter through the reaction
of Singapore, Kent Ridge, Singapore 119260 of the chlorosilyl group with the silanol group. The transmission
ReceiVed June 22, 2006 electron microscopy (TEM) image of the initiator-immobilized
ReVised Manuscript ReceiVed December 1, 2006 silica nanoparticles (Figure 1a) shows that the surface-modified
nanoparticles remain unagglomerated. The X-ray photoelectron
1. Introduction spectroscopy (XPS) wide-scan spectrum (Figure 2a) and energy-
Hollow micro/nanospheres are potentially useful as encap- dispersive X-ray (EDX) analysis results (Figure 3a) of the
sulants for drugs,1-3 catalysts,4 paints,4 and enzymes,3 as surface-modified nanoparticles indicate that the benzyl chloride
transducers for electronics,5 and as absorption materials for initiators have been successfully immobilized on the silica
sound.5 To meet the demand for encapsulation, hollow spheres surface. A chlorine content of about 1.44 wt % for the SiO2-
of carbon,6,7 polymers,8,9 metal,10,11 and inorganic materials1,12-14 initiator nanospheres was obtained from elemental analysis. The
have been prepared using polymeric or inorganic spherical corresponding surface benzyl chloride initiator concentration (F)
particles as templates. The century-old polyaniline (PANI) has of 2.4 initiators/nm2 is comparable to the reported silane initiator
been of particular interest because of its good environmental density of 2.6 initiators/nm2 for the silica particle surface.37
stability,16,17 controllable electrical conductivity,18-20 and the Using the average cross-sectional area (A) of about 2 nm2 for
ability to exist in a number of intrinsic redox states.21,22 The the vinyl and acrylate polymer brushes prepared via ATRP,44
unique physicochemical and solution-processable properties of the surface initiator efficiency of the present system (1/FA) is
the aniline polymers make them potentially useful for application estimated to be about 21%.
in energy storage devices,23 optoelectronic devices,24 display The silica-graft-poly(4-vinylaniline) (SiO2-g-PVAn) nano-
devices,25 electrodes and sensors,26,27 corrosion protection of spheres were prepared via surface-initiated ATRP of 4-vinyl-
metals, and drug delivery.28 Accordingly, the preparation of aniline (VAn) from the initiator-immobilized silica nanoparticles,
PANI hollow nanospheres should be of interest and importance. using CuCl and N,N,N′,N′′,N′′-pentamethyldiethylenetriamine
Excellent works on PANI hollow micro- and nanospheres, (PMDETA) as the catalyst system. The characteristics of the
prepared from self-assembly and coating of PANI on emulsion, SiO2-g-PVAn nanospheres prepared under different ATRP
colloidal polystyrene, polyeletrolyte, and metal oxide templates, durations are summarized in Table 1. The chain length of PVAn
are available in the literature.29-35 brushes, and thus the thickness of the PVAn shell, on the silica
Recent development in surface-initiated controlled/living nanospheres can be adjusted by changing the ATRP time. The
polymerization has provided an alternative approach to the number-average molecular weight (Mn) of PVAn, cleaved via
preparation of inorganic-organic core-shell hybrids with well- HF etching, from the SiO2-g-PVAn nanoparticles increases from
defined and controlled shell structures.36-40 Nearly monodis- 1.4 × 103 to 5.2 × 103 g/mol with the increase in polymerization
persed hollow spheres with controllable shell thickness can be time from 1.5 to 6 h, while the polydispersity index remains at
prepared from the removal of the core templates of these core- around of 1.2 (Table 1). Table 1 also shows the theoretical Mn’s
shell composites.11,41,42 In this study, we report on a surface- of the PVAn brushes calculated from the initiator efficiency
initiated living radical polymerization approach to the prepa- and density, the thickness of PVAn film, and the PVAn density
ration of well-defined PANI hollow nanospheres. The strategy of about 1 g/cm3. They are comparable to those obtained from
is shown in Scheme 1. Initially, the atom transfer radical GPC measurements. Figure 2b shows the XPS wide-scan
polymerization (ATRP) initiator, trichloro(4-chloromethylphe- spectrum of the SiO2-g-PVAn1 nanospheres described in Table
nyl)silane, was immobilized on the surface of SiO2 nanoparticles 1. Prior to XPS analysis, the SiO2-g-PVAn nanospheres were
of about 25 nm diameter. Silica nanoparticles with surface- washed with copious amounts of THF, a good solvent for PVAn.
grafted polymer of 4-vinylaniline (SiO2-g-PVAn) were prepared The exhaustive washing procedures ensured the complete
via surface-initiated ATRP of 4-vinylaniline (VAn). Subsequent removal of PVAn homopolymer absorbed on the SiO2-g-PVAn
surface oxidative graft copolymerization of aniline, using the nanospheres. The appearance of strong C 1s and N 1s signals,
aniline moieties of PVAn as the anchoring sites,43 and removal as well as an N 1s spectrum with line shape and binding energy
of the silica cores by HF etching produced the well-defined (399.4 eV) characteristic of those of the -NH2 species43 (inset
P(VAn-graft-PANI) hollow nanospheres with a conductive shell of Figure 2b), suggests that PVAn has been successfully grafted
of about 15-40 nm in thickness and core void of about 25 nm on the silica nanospheres. The persistence of the Si 2s and Si
in diameter. The present approach allows the preparation of 2p signals, albeit of substantially reduced intensities, in the XPS
conductive PANI hollow nanospheres of controllable dimension analysis is consistent with the presence of core-shell structured
SiO2-g-PVAn1 nanospheres having a PVAn shell thickness of
* To whom correspondence should be addressed: e-mail fu7352@ about 3 nm,45 which is less than the sampling depth of the XPS
seu.edu.cn (G.D.F.), [email protected] (E.T.K.); Tel +65-65162189; Fax technique (∼7.5 nm in an organic matrix46).
+65-67791936.
† Southeast University. Surface-initiated oxidative graft copolymerization of aniline
‡ National University of Singapore. from the SiO2-g-PVAn nanospheres, using the aniline moieties
10.1021/ma0613988 CCC: $37.00 © 2007 American Chemical Society
Published on Web 02/17/2007
2272 Notes Macromolecules, Vol. 40, No. 6, 2007

of PVAn as the anchoring site,43 produced the silica-graft-poly-

(4-vinylaniline-g-polyaniline), or SiO2-g-P(VAn-g-PANI), core-
shell nanospheres. The effect of grafted PVAn chain length on
a solid substrate on the subsequent extent of oxidative graft
copolymerization of aniline has been reported earlier.47 Figure
1b shows the TEM image of the SiO2-g-P(VAn-g-PANI)1
nanospheres of Table 1. Basically, a core-shell structure (dark-
colored SiO2 core and light-colored P(VAn-g-PANI) shell) was
obtained. The disappearance of the Si signals in the XPS wide-
scan spectrum of the SiO2-g-P(VAn-g-PANI)1 nanospheres
(Figure 2c) is consistent with the presence of a SiO2-g-P(VAn-
g-PANI) core-shell structure, with a shell thickness greater than
the sampling depth of the XPS technique.46 The presence of
PANI chains in the shell of the SiO2-g-P(VAn-g-PANI) nano-
sphere was also indicated by the marked increase in the C and
N concentration, relative to the Si concentration, over those of
the original SiO2-g-PVAn nanospheres (compare the EDX
spectra of Figure 3b,c). The atomic sensitivity of the Cu 2p
signal is about 5 times that of the C 1s signal. Thus, any trace
amount of Cu (down to 0.02 at. %) in the sample could still be
detected by XPS.48 The absence of Cu signals in the XPS and
EDX analysis results of the SiO2-g-PVAn and SiO2-g-P(VAn-
g-PANI) nanospheres indicates that the CuCl catalyst for ATRP
has been completely removed during the process of precipitating
SiO2-g-PVAn nanospheres in methanol and subsequent oxidative
graft copolymerization of aniline in an acid medium (see
Experimental Section).
HF etching of the SiO2-g-P(VAn-g-PANI) nanoparticles
removed the SiO2 cores and produced the HF-doped P(VAn-
g-PANI) hollow nanospheres. The TEM image (Figure 1c) of
the HF-etched SiO2-g-P(VAn-g-PANI)1 nanospheres of Table
1 clearly reveals the hollow structure of nanospheres with a
shell thickness of about 16 nm. Structural integrity of the shell
or capsule is probably enhanced by the entangled PANI brushes
as well as the cross-linked PANI chains from side reactions.49
The almost disappearance of the Si signal and the predominance
of carbon and nitrogen signals in the EDX spectrum of the
hollow nanospheres in Figure 3d are consistent with the
successful removal of the silica cores and the formation of
P(VAn-g-PANI) hollow nanospheres. The persistence of a trace
amount of Si in the P(VAn-g-PANI) hollow nanospheres (Figure
3d) after HF treatment suggests that the Si-O-Si bridges
between the trifunctional initiation sites remain intact to provide
a link for the end-attached chains. P(VAn-g-PANI) hollow
nanospheres of different shell thicknesses are shown in the insets
of Figure 1c, and their characteristics are also summarized in
Table 1. With the increase in oxidative graft copolymerization
time of aniline from 0.5 to 4 h, the shell thickness of the hollow
nanospheres has increased correspondingly from 16 to 41 nm.
For the hollow nanosheres with a thin P(VAn-g-PANI) shell
(Figure 1c), a slight expansion of the hollow core has occurred
Figure 1. Transmission electron microscopy (TEM) images of after the HF etching of the SiO2 core. Nevertheless, the thin
(a) the trichloro(4-chloromethylphenyl)silane-immobilized silica shell consisting of dense comb-shaped P(VAn-g-PANI) chains
nanoparticles and the silica-graft-poly(4-vinylaniline-graft-poly-
aniline) [SiO2-g-P(VAn-g-PANI)1 nanospheres in Table 1, pre- with entangled or cross-linked49 PANI brushes remained intact.
pared from silica-graft-poly(4-vinylaniline) nanospheres, or SiO2-g- The self-assembled and HF protonated P(VAn-g-PANI) hollow
PVAn1 nanospheres, of Table 1 via 0.5 h of oxidative graft nanospheres exhibit conductivity in the range of 10-2-10-1 S
copolymerization of aniline] (b) before and (c) after HF etching. cm-1 (Table 1), or about 1-2 orders of magnitude lower than
Theinsets in (c) are the TEM images of hollow nanospheres
with different shell thickness, derived from (c′) SiO2-g- that of the protonated aniline homopolymer.19 The apparently
P(VAn-gPANI)2 nanospheres in Table 1 [prepared from SiO2-g- lower conductivity for the self-assembled hollow nanospheres
PVAn1 nanospheres of Table 1 via 1.5 h of oxidative graft co- can be attributed to the presence of core voids and interstitial
polymerization of aniline] and (c′′) SiO2-g-P(VAn-g-PANI)3 spaces in the layer. The conductivity of the self-assembled PANI
nanospheres in Table 1 [prepared from SiO2-g-PVAn1 nano-
spheres of Table 1 via 4 h of oxidative graft copolymerization of hollow nanospheres is also lower than that of the PANI pellets
aniline]. from compressed PANI hollow nanospheres.
Macromolecules, Vol. 40, No. 6, 2007 Notes 2273

Figure 2. X-ray photoelectron spectroscopy (XPS) wide-scan spectra of the (a) trichloro(4-chloromethylphenyl)silane-immobilized silica nanospheres,
(b) silica-graft-poly(4-vinylaniline) nanospheres [SiO2-g-PVAn1 nanospheres in Table 1 from 1.5 h of surface-initiated atom transfer radical
polymerization of 4-vinylaniline], and (c) silica-graft-poly(4-vinylaniline-graft-polyaniline) nanospheres [SiO2-g-P(VAn-g-PANI)1 nanospheres in
Table 1 from 0.5 h of oxidative graft copolymerization of aniline with the SiO2-g-PVAn1 nanosphere surface]. XPS N 1s core-level spectra of the
P(VAn-g-PANI) hollow nanospheres [from HF etching of the SiO2-g-P(VAn-g-PANI)1 nanospheres in Table 1] in their (d) HF-protonated (as-
prepared) form, (e) EM base form, (f) LM base form, and (g) 1 M H2SO4 reprotonated EM form.

Scheme 1. Preparation of Conductive Poly(4-vinylaniline-graft-polyaniline), or P(VAn-g-PANI), Hollow Nanospheres via

Surface-Initiated Atom Transfer Radical Polymerization (ATRP) and Oxidative Graft Copolymerizationa

a
THF ) tetrahydrofuran, Et3N ) triethylamine, and VAn ) 4-vinylaniline.

The TEM images indicate that the PANI hollow nanospheres amine (-NH-), and the positively charged nitrogen (N+).21 The
can undergo interconversion among the various intrinsic redox presence of about equal amount of the imine and amine
states while maintaining the hollow nanospherical structure. components in Figure 2e is consistent with the 50% intrinsically
Parts d-g of Figure 2 show the N 1s core-level spectra of the oxidized state of the EM base. The single nitrogen environment
PANI hollow nanospheres (from SiO2-g-P(VAn-g-PANI)1 of at the BE of about 399.4 in Figure 2f indicates that the PANI
Table 1) in their HF-protonated (as prepared) form, neutral EM hollow nanosperes have been converted to the fully reduced
base form, fully reduced leucoemeraldine (LM) base form, and LM state. Reprotonation of the EM base by H2SO4 has resulted
the H2SO4-reprotonated EM base (EM-H2SO4) form, respec- in the disappearance of the )N- species and the appearance
tively. The peak components at BEs of about 398.2, 399.4, and of a corresponding amount of the N+ species (Figure 2g), as
>400 eV correspond to the quinonoid imine (dN-), benzenoid protonation occurred preferentially at the imine nitrogen.19-21
2274 Notes Macromolecules, Vol. 40, No. 6, 2007

copolymerization time. Obviously, the dimension of the hollow

cores could be further controlled by changing the size of the
initiator-immobilized silica nanoparticles. The resulting PANI
hollow nanospheres exhibited intrinsic redox states and depro-
tonation/reprotonation behavior characteristic of those of the
aniline homopolymer.
4. Experimental Section
Initiator Immobilization on Silica Nanoparticles. Dried SiO2
nanoparticles (2.0 g) of about 25 nm diameter, 3.0 g (9.5 mmol) of
trichloro(4-chloromethylphenyl)silane (97%), and 20 mL of abso-
lutely dried THF were introduced into a two-necked flask. Tri-
ethylamine (1.2 mL, 8.6 mmol) in THF (5.0 mL) was added
dropwise, with stirring, under an argon atmosphere. The reaction
mixture was left to stand for 8 h and then exposed to air for another
18 h. After five cycles of ethanol and THF rinsing, and separation
by centrifugation, about 1.8 g of white initiator-immobilized SiO2
nanoparticles was obtained. The chlorine concentration was about
1.44 wt %, as determined from elemental analysis. This chlorine
concentration corresponded to about 2.4 benzyl chloride initiators
per nm2 of the particle surface.44
Surface-Initiated Atom Transfer Radical Polymerization
(ATRP) of 4-Vinylaniline. About 0.1 g of the initiator-immobilized
silica nanoparticles, 1.2 mL (9 mmol) of 4-vinylaniline (VAn, 90%),
1 mL of dry THF, and 4 mg (0.04 mmol) of CuCl (99.7%) were
introduced into a dry Pyrex test tube. After purging with argon for
20 min, about 0.04 mmol of N,N,N′,N′′,N′′-pentamethyldiethylen-
etriamine (PMDETA, 99%) was added, and the reaction tube was
sealed with a rubber stopper. Thus, the molar ratio of [4-vinyl-
anilne]:[initiator]:[CuCl]:[PMDETA] was about 225:1:1:1. Surface-
initiated ATRP was carried out under continuous stirring at
110 °C. The reaction time was varied from 1.5 to 6 h. At the end
of each reaction, the reaction mixture was diluted with 5 mL of
THF, and the product was precipitated into 100 mL of methanol.
The product was redispersed into 10 mL of THF and centrifuged
to remove the physically adsorbed 4-vinylaniline homopolymer.
The process was repeated another two times.
Oxidative Graft Copolymerization of Aniline. About 0.1 g of
the 4-vinylaniline polymer (PVAn) grafted SiO2 nanospheres, or
SiO2-g-PVAn nanospheres, and 1 mL (0.01 mol) of aniline were
introduced slowly into 30 mL of 1.0 M HCl under magnetic stirring.
About 0.6 g (2.6 mol) of (NH4)2S2O8 was dissolved in 20 mL of
1.0 M HCl. The oxidant solution was introduced into the SiO2-g-
PVAn and aniline reaction mixture at 0 °C. The oxidative graft
Figure 3. Energy-dispersive X-ray (EDX) analysis spectra of (a) the copolymerization was carried out for 0.5-4 h. The aniline moiety
trichloro(4-chloromethylphenyl)silane-immobilized silica nanoparticles, of the VAn units served as the anchoring and initiation sites for
(b) the silica-graft-poly(4-vinylaniline) nanospheres [SiO2-g-PVAn1 the oxidative graft copolymerization of aniline.43 The polyaniline
nanospheres in Table 1 from 1.5 h of surface-initiated atom transfer (PANI) in the shell was then converted to the neutral emeraldine
radical polymerization of 4-vinylaniline], and the silica-graft-poly(4- (EM) base by treatment with excess 0.5 M NaOH. The product
vinylaniline-graft-polyaniline) nanospheres [SiO2-g-P(VAn-g-PANI)1 was redispersed into 1-methyl-2-pyrrolidone (NMP, a good solvent
nanospheres in Table 1 from 0.5 h of oxidative graft copolymerization for EM base21), and centrifuged to remove the adsorbed PANI
of aniline with the SiO2-g-PVAn1 nanosphere surface] (c) before and homopolymer in its EM base form. The process was repeated
(d) after HF treatment. Insets c′ and c′′ show the TEM images of the several times until no PANI homopolymer was found in the NMP
hollow nanospheres obtained from HF etching of the respective SiO2-
g-P(VAn-g-PANI)2 nanospheres [from 1.5 h of oxidative graft co- solutions. The SiO2 cores were removed by immersing the SiO2-
polymerization of aniline with the SiO2-g-PVAn1 nanosphere surface] g-P(VAn-g-PANI) nanospheres into 10% HF for 24 h. Intercon-
and SiO2-g-P(VAn-g-PANI)3 nanospheres [from 4 h of oxidative graft versions among the various intrinsic redox and protonation states
copolymerization of aniline with the SiO2-g-PVAn1 nanosphere surface] of the PANI hollow nanospheres were carried out as previous
of Table 1. described.19-22 Thus, the protonated PANI was converted to the
EM base by treatment with 0.5 M NaOH, the EM base to the fully
3. Conclusions reduced leucoemeraldine (LM) base by treatment with phenylhy-
In summary, a controlled polymerization approach to the drazine, and the EM base to the reprotonated PANI by treatment
preparation of polyaniline (PANI) hollow nanospheres was with 1 M H2SO4.
described. Surface-initiated atom transfer radical polymerization Characterization. Gel permeation chromatography (GPC) was
performed on an HP 1100 high-pressure liquid chromatography
(ATRP) of 4-vinylaniline (VAn) from the initiator-immobilized
(HPLC), equipped with a HP 1047A refractive index detector and
SiO2 nanoparticles and subsequent oxidative graft copolymer- a PLgel MIXED-C 300 × 7.5 mm column (packed with 5 µm
ization of aniline allowed the preparation of well-defined SiO2- particles of different pore size). The column packing allowed the
g-P(VAn-g-PANI) core-shell structures. Conductive P(VAn- separation of polymers over a wide molecular weight range of 200-
g-PANI) hollow nanospheres with different shell thickness could 3 000 000. THF was used as the eluent at a flow rate of 1 mL/min
be readily prepared by varying the ATRP and the oxidative graft at 35 °C. Polystyrene standards were used as the references. XPS
Macromolecules, Vol. 40, No. 6, 2007 Notes 2275

Table 1. Characteristics of the Conductive Polyaniline Hollow Nanospheres

conductivity
particle shell shell
polymerization mol wta mol wtd sizee thicknesse thicknessf σ1g σ2h
sample time (h) (g/mol) PDIa (g/mol) (nm) (nm) (nm) (S/cm) (S/cm)
SiO2-g-PVAn1b 1.5 1.4 × 103 1.16 2.0 × 103 3
SiO2-g-PVAn2b 3.0 2.5 × 103 1.23 3.9 × 103 5
SiO2-g-PVAn3b 6.0 5.2 × 103 1.18 7.5 × 103 9
SiO2-g-P(VAn-g-PANI)1c 0.5 61 14 16 2 × 10-2 8 × 10-2
SiO2-g-P(VAn-g-PANI)2c 1.5 83 24 26 3 × 10-2 2 × 10-1
SiO2-g-P(VAn-g-PANI)3c 4.0 111 44 41 1 × 10-1 3 × 10-1
a Number-average molecular weight of poly(4-vinylaniline), or PVAn, obtained from HF etching of the corresponding nanospheres. PDI ) polydispersity

index (weight-average molecular weight/number-average molecular weight or Mw/Mn). b Silica-graft-poly(4-vinylaniline) nanospheres prepared from the
initiator-immobilized silica nanospheres at a molar feed ratio of [4-vinylaniline]:[initiator]:[CuCl]:[PMDETA] ) 225:1:1:1. The amount of initiator on the
SiO2 surface was determined by element analysis. PMDETA ) N,N,N′,N′′,N′′-pentamethyldiethylenetriamine; initiator ) trichloro(4-chloromethylphenyl)silane.
c Silica-graft-poly(4-vinylaniline-graft-polyaniline) nanospheres obtained from the SiO -g-PVAn1 nanospheres via oxidative graft copolymerization of aniline.
2
d Theoretical values calculated from the initiator efficiency and density and film thickness of surface-initiated ATRP of 4-vinylaniline. e Average shell

thickness and particle size of SiO2-g-P(VAn-g-PANI) determined from transmission electron microscope (TEM) image before HF treatment. The shell
thickness of SiO2-g-PVAn was estimated simulation. f Average shell thickness determined from TEM image after HF treatment. g Conductivity of self-
assembled, HF-protonated hollow nanospheres. h Conductivity of compressed/compacted nanospheres in pellet form.

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