Chem. Mater.

2001, 13, 581-587 581

Synthesis and Characterization of Poly(ethylene

glycol)-Grafted Polyaniline
Peng Wang and K. L. Tan
Department of Physics, National University of Singapore, Kent Ridge, Singapore 119260

Fu Zhang, E. T. Kang,* and K. G. Neoh

Department of Chemical Engineering, National University of Singapore,
Kent Ridge, Singapore 119260
Received October 24, 2000. Revised Manuscript Received December 4, 2000

Poly(ethylene glycol) (PEG)-grafted polyaniline (PANi) copolymers were prepared by

incorporating a chlorine end-capped methoxy PEG (mPEGCl) of molecular weight of about
2000 onto the leucoemeraldine form of PANi via N-alkylation. The microstructures and
compositions of the mPEG-grafted PANi (mPEG-g-PANi) copolymers were characterized by
FT-IR, elemental analysis, UV-visible absorption spectroscopy, thermogravimetric (TG)
analysis and X-ray photoelectron spectroscopy (XPS). The graft concentration (degree of
N-alkylation) can be controlled by adjusting the molar feed ratio of mPEGCl to the number
of repeat units of PANi. The mPEG-g-PANi copolymers showed enhanced solubility in
common organic solvents and water. The electrical conductivity of the mPEG-g-PANi
copolymer film decreased by a factor of 5 at the mPEG graft concentration of 0.05. The mPEG-
g-PANi copolymer with a high graft concentration was very effective in preventing platelet
adhesion.

Introduction characteristic is believed to have resulted from the

Recent investigations1
into the century-old2,3
aniline stiffness of the polymer backbone and the hydrogen-
family of polymers have rekindled intense research bonding interaction between adjacent chains. The lim-
interest in these materials. The aniline polymers gener- ited solubility has impeded not only its industrial
ally have controllable electrical conductivity, environ- applications but also a complete understanding of the
mental stability, and interesting redox properties as- polymer structure.6 Great effort has been devoted to the
sociated with the chain nitrogens.4 They have been modification of the aniline polymers with various func-
extensively studied for their unique characteristics and tional groups to enhance their processability. For ex-
potential applications in electrical devices, such as ample, self-doped PANi with sulfonic acid groups sub-
polymer electrodes and sensors. The aniline polymers stituted onto the aniline ring has been synthesized by
have the general formula [(-B-NH-B-NH-)y(-B- treating EM base with fuming sulfuric acid.7,8 Co-
NdQdN-)1-y]x, in which B and Q denote the C6H4 rings polymerization of aniline with o-alkoxyaniline has been
in the benzenoid and quinonoid forms, respectively. carried out to produce soluble, conductive polymers.9
Thus, the aniline polymers are basically poly(p-phen- Flexible alkyl chains have been incorporated into PANi
yleneamine)s, in which the intrinsic oxidation states can through N-alkylation of the LM base form. It was found
vary from that of the fully reduced leucoemeraldine that the solubility of the polymer in common organic
(LM, y ) 1), through that of the 50% intrinsically solvents improved remarkable with alkylation.10 On the
oxidized emeraldine (EM, y ) 0.5), to that of the fully other hand, Mikhael et al.11 reacted EM base and its
oxidized pernigraniline (PNA, y ) 0). The polymer can anions with various alkylating and acylating agents.
achieve its highly conductive state either through the Poly(ethylene glycol) (PEG) is gaining wide recogni-
protonation of the imine nitrogens (dN-) in its EM tion as it possesses many unique physical and biochemi-
oxidation state, or through the oxidation of the amine cal properties, such as nontoxicity, biocompatibility, and
nitrogens (-NH-) in its fully reduced LM state.5 miscibility with many solvents.12 Therefore, PEG and
The emeraldine form of PANi is obtained as a dark its derivatives are finding an ever-expanding range of
powder which exhibits only limited processability. This (6) Li, S.; Cao, Y.; Xue, Z. Synth. Met. 1987, 20, 141.
(7) Yue, J.; Wang, Z. H.; Cromack, K. R.; Epstein, A. J.; Mac-
* Fax: (65) 779-1936. E-mail: cheket@nus.edu.sg. Diarmid, A. G. J. Am. Chem. Soc. 1991, 113, 2665.
(1) MacDiarmid, A. G.; Chiang, J. C.; Richter, A. F; Epstein A. J. (8) Kang, E. T.; Neoh, K. G.; Woo, Y. L.; Tan K. L. Polym. Commun.
Synth. Met. 1987, 18, 285. 1990, 32, 412.
(2) Green, A. G.; Woodhea, A. E. J. Chem. Soc. 1910, 1117. (9) Liao, Y. H.; Angelopoulos, M.; Levon, K. J. Polym. Sci. Part A:
(3) Green, A. G.; Woodhea, A. E. J. Chem. Soc. 1910, 2388. Polym Chem. 1995, 33, 2725.
(4) Kang, E. T.; Neoh, K. G.; Tan, K. L. Prog. Polym. Sci. 1998, 23, (10) Zheng, W. Y.; Levon, K.; Laakso, J.; Österholm, J. E. Macro-
277. molecules 1994, 27, 7754.
(5) Ray, A.; Asturias, G. E.; Kershner, D. L.; Richter, A. F.; (11) Mikhael, M.; Padius, A. B.; Hall, H. K. J. Polym. Sci. Part A:
MacDiarmid, A. G.; Epstein, A. J. Synth. Met. 1989, 29, E141. Polym. Chem. 1994, 27, 7754.

10.1021/cm000829c CCC: $20.00 © 2001 American Chemical Society

Published on Web 02/01/2001
582 Chem. Mater., Vol. 13, No. 2, 2001 Wang et al.

biomedical and industrial applications.13 In addition, dissolved. A solution of methylsufinyl carbanion in DMSO was
PEG has also found useful applications in secondary formed as described in the literature.10,17 About 0.4 g (0.0044mol)
lithium polymeric batteries.14 Thus, incorporating PEG of LM powder was added to the sodium methylsufinyl carban-
ion solution at 60 °C. A dark-yellow anion solution formed after
into PANi may endow the century-old aniline polymer 4 h of reaction time. The solution was cooled to 40 °C, and a
with new and interesting properties. For instances, the predetermined amount of mPEGCl was added with vigorous
process may enhance the solution, including aqueous stirring. The amount of mPEGCl added dictated the resulting
solution, and the processability of PANi, as well as copolymer composition. The color of the solution turned blue
improve the biocompatibility of PANi for applications gradually, suggesting the oxidation of the LM backbone to the
as biosensors or as biomedical materials for implants. EM state.4 The reaction was allowed to continue for 24 h.
In the present work, we report on the synthesis and Separation and Purification of the Copolymer Adduct.
Different separation and purification methods were adopted
characterization of PEG-grafted polyaniline. according to whether the product was soluble in water or not.
The water solubility, in turn, was determined by the concen-
Experimental Section tration of the grafted mPEG chains. For the product that was
insoluble in water, the reaction mixture was poured into a 10-
1. Materials. Anhydrous-grade dimethyl sulfoxide (DMSO) times excess volume of doubly distilled water, under vigorous
was obtained from Merck Chemical Co. Aniline, thionyl stirring, to precipitate the copolymer. The precipitate was
chloride (SOCl2), sodium hydride (NaH), methoxy poly- recovered by filtration and washed exhaustively with doubly
(ethylene glycol) (mPEG) with a molecular weight of about distilled water to remove the residual amount of unreacted
2000, and all other reagent-grade chemicals were purchased species. The product so obtained was dried under reduced
from Aldrich Chemical Co. and were used as received. pressure at ambient temperature. For the product that was
2. Preparation of the Graft Copolymer. Chlorine End- soluble in water, the reaction mixture was first precipitated
Capped mPEG (mPEGCl). mPEG (10 g, 0.005 mol) was into a large excess of diethyl ether. The precipitate was
dissolved in 40 mL of CCl4, containing also 0.005 mol of dry dialyzed against doubly distilled water for 48 h. The water
pyridine. Thionyl chloride (0.015 mol), dissolved in 10 mL of was allowed to evaporate under reduced pressure at ambient
CCl4, was added dropwise over a period of 1 h under reflux. temperature. The product was then collected and subjected to
The mixture was stirred at 60 °C overnight. The pyridine salt further drying under reduced pressure. The copolymer samples
was removed by filtration. The CCl4 and excess SOCl2 were were characterized by elemental analysis, FT-IR spectroscopy,
removed by pumping under reduced pressure. The adduct was UV-visible absorption spectroscopy, thermogravimetric (TG)
dissolved in CH2Cl2, dried over anhydrous K2CO3, and filtered. analysis, and X-ray photoelectron spectroscopy (XPS).
The filtrate was precipitated into 10-fold excess of cold diethyl Preparation of Copolymer Thin Films. The copolymer samples
ether. The chlorinated mPEG (or mPEGCl) precipitated out were dissolved in NMP to form the 1 wt % solutions. The
as a white powder and was dried under reduced pressure for solutions were cast onto glass plates and heated in a constant
24 h.15,16 The chlorination of mPEG was studied by both the temperature oven at 110 °C for 2 h to form lightly cross-linked
FT-IR absorption spectroscopy and the elemental analysis. The films, similar to the method used for the preparation of PANi
chlorine end-capped mPEG (mPEGCl) can be identified from films.18 The films so obtained were dried under reduced
the changes in the IR absorption characteristics. The OH pressure at room temperature for 24 h to remove the NMP.
absorption band for mPEG in the 3300-3500 cm-1 region has Platelet Adhesion. Heparinized blood from a healthy dog
disappeared, with the corresponding appearance of the C-Cl (supplied by the Animal Holding Unit, National University of
absorption band at 671 cm-1. On the other hand, elemental Singapore) was used in this study. The blood was centrifuged
analysis reveals the presence of 1.6 wt % of Cl in the at 200 G for 15 min to obtain the platelet-rich plasma (PRP).
compound. The result suggests that about 90% of the mPEG The PRP was diluted with PBS to give a concentration of about
molecules have been converted to mPEGCl. 1 × 105 platelets/µL. About 0.1 mL of the diluted platelet
Synthesis of the mPEG-Grafted Polyaniline (mPEG-g-PANi) suspension was placed onto the polymer film surface of about
Copolymers. Polyaniline was synthesized by oxidative poly- 0.8 cm × 0.8 cm in area. The film was incubated at 37 °C for
merization of aniline according to the method reported in the 30 min under a static condition. After incubation, the film
literature.4,5 Thus, 0.05 mol of aniline was dissolved in 800 surface was rinsed with PBS gently, but thoroughly, to remove
mL of 1 M HCl. The solution was kept at 0 °C under an argon the loosely adhered platelets on the film surface. After the
atmosphere. A prechilled solution of 0.05 mol of ammonium thorough rinsing with PBS, the films were allowed to dry at
persulfate in 200 mL of 1 M HCl was added slowly with room temperature.19
vigorous stirring. The reaction mixture was agitated continu- 3. Physical Measurement. FT-IR spectra of the polymer
ously for another 5 h. The precipitate was subsequently filtered and copolymer powders were obtained from a Bio-Rad FTS 135
and collected. It was converted to the EM base by treatment FT-IR spectrophotometer. Each spectrum was collected by
with excess 0.5 M aqueous NH4OH and dried by pumping cumulating 16 scans at a resolution of 4 cm-1. The UV-visible
under reduced pressure. The fully reduced LM was prepared absorption spectra of the polymer and copolymer solutions or
by treating the EM base powders with hydrazine in ethanol thin films coated onto quartz substrates were monitored on
for 24 h under an argon atmosphere. The light gray LM an UV-vis-NIR scanning spectrophotometer (Shimadzu UV-
powders were washed thoroughly with ethanol and THF, in 3101 PC). The bulk C and N atomic ratios were determined
that order, to remove the excess reducing agent and the low- by elemental analyses on a Perkin-Elmer 2400 elemental
molecular-weight LM species. The LM powders were then analyzer. The Cl content was determined, on the other hand,
dried under reduced pressure at room temperature. by the Schöniger combustion method20 at the Microanalysis
A 40 mL aliquot of DMSO and 0.115 g (0.0048 mol) of NaH Centre of the National University of Singapore. For the TG
were introduced into a 100 mL round-bottom flask. The analysis, the polymer and copolymer samples were heated to
reaction flask was kept under an inert atmosphere throughout 700 °C at a heating rate of 20 °C/min under a dry nitrogen
the subsequent reactions by a constant flow of argon. The atmosphere in the Du Pont thermal analyst 2100 system,
mixture was stirred at 60 °C until the NaH was completely equipped with a TGA 2050 thermogravimetric thermal ana-

(12) Lee, J. H.; Lee, H. B.; Andrade, J. D. Prog. Polym. Sci. 1995, (17) Takayanagi, M.; Katagose, T. J. Polym. Chem. Ed. 1981, 19,
20, 1043. 1133.
(13) Harris, J. M. J. Macromol. Sci. RMCP 1983, C25 (3), 325. (18) MacDiarmid, A. G.; Min, Y.; Wiesinger, J. M.; Oh, E. J.; Scherr,
(14) Novak, P.; Müller, K.; Santhanam, K. S. V.; Haas, O. Chem. E. M.; Epstein, A. J. Synth. Met. 1993, 55, 753.
Rev. 1997, 97, 207. (19) Kulik, E.; Ikada, Y. J. Biomed. Mater. Res. 1996, 30, 295.
(15) Zalipsky, S.; Gilon, C.; Zilkha, A. Eur. Polym. J. 1983, 19, 1177. (20) Walton, H. F. Principles and Methods of Chemical Analysis,
(16) Ha, C. S.; Choi, H. Y.; Cho, W. J. Polym. Bull. 1991, 25, 185. 2nd ed.; Prentice-Hall: Englewood Cliffs, NJ, 1964; pp 175-178.
Poly(ethylene glycol)-Grafted Polyaniline Chem. Mater., Vol. 13, No. 2, 2001 583

the graft concentration is defined as the number of

mPEG units (of MW ∼2000) per aniline unit of PANi.
It can be seen that the graft concentration increases
with the increase in feed molar ratio of the mPEGCl to
aniline units.
The fully reduced LM was used in this study in order
to avoid the side reactions, such as the cross-linking
reaction.11 The LM dissolves well in DMSO in the
presence of NaH. The blue product formed during the
grafting reaction indicates the presence of autoxidation4
of the aniline polymer backbone. The changes in intrin-
sic oxidation states ([dN-]/[-NH-] ratios) of PANi are
revealed by FT-IR spectroscopy and XPS. Figure 2
shows the FT-IR spectra of the LM base, the EM base
and the mPEG-g-PANi base (graft concentration )
0.046) powders. The absorption peaks at 1595 and 1503
cm-1 are attributable to the quinoid unit and benzenoid
unit of PANi, respectively.21 The predominance of the
absorption band at 1503 cm-1 for the LM base is
consistent with the fully reduced nature of the LM state
of PANi. On the other hand, the approximately equal
intensities for the 1595 and 1503 cm-1 bands for the
EM base are consistent with a 50% intrinsically oxidized
PANi structure. For the spectrum of the mPEG-g-PANi
sample, two new absorption bands have appeared. They
Figure 1. Schematic diagram illustrating the synthesis of the correspond to that at 952 cm-1 for the methylene
mPEG-g-PANi graft copolymer.
rocking mode and that at 1105 cm-1 for the C-O-C
lyzer. The electrical conductivity of the cross-linked polymer stretching mode. These are the typical absorption bands
films was measured by the four-probe method. XPS measure- of PEG.15 In addition, the intensity of the absorption
ments were made on a VG ESCALAB MkII spectrometer with band at 1595 cm-1 from the original LM base has
a Mg KR X-ray source (1253.6 eV photons) at a constant retard become comparable to that of the absorption band at
ratio of 40. The polymer films were mounted on the standard 1503 cm-1, suggesting an increase in the intrinsic
sample studs by means of double-sided adhesive tapes. The oxidation state of LM compared to that of EM during
core-level signals were obtained at the photoelectron takeoff
angle (R, with respect to the sample surface) of 75°. The X-ray
the grafting and purification processes. The phenom-
source was run at a reduced power of 120 W. The pressure in enon is commonly observed in reactions involving LM,
the analysis chamber was maintained at 7.5 × 10-9 Torr or especially in the presence of oxygen.4 The auto-oxidation
lower during each measurement. All binding energies (BEs) effect can be minimized by carrying out the purification
were referenced to the C1s neutral carbon peak at 284.6 eV. of the copolymers under an inert atmosphere. Neverthe-
In peak synthesis, the line width (full width at half-maximum, less, the oxidation of the copolymer backbone to the EM
or fwhm) for the Gaussian peaks was maintained constant for
state is inconsequential as the subsequent characteriza-
all components in a particular spectrum. Surface elemental
stoichiometries were determined from peak-area ratios and tion, processing, and application of the copolymers are
were reliable to (10%. The static water contact angles of cross- carried out under atmospheric conditions.
linked polymer thin films were measured at 25 °C and 60% Figure 3a-e shows the UV-visible absorption spectra
relative humidity using a sessile drop method in a telescopic of the LM and EM bases and three mPEG-g-PANi
goniometer (Rame-Hart model 100-00(230)). The telescope samples (graft concentration ) 0.023, 0.046, and 0.257,
with a magnification power of 23× was equipped with a
protractor of 1° graduation. For each angle reported, at least
respectively) in NMP. For the LM base, only one
five sample readings from different surface locations were absorption peak at 340 nm, which originates from the
averaged. The angles reported were reliable to (3°. The π-π* transition of the benzenoid rings,22 is observable.
adhered platelets on the polymer film surface were studied For the EM base and the mPEG-g-PANi samples, each
by scanning electron microscopy (SEM), using a JEOL 6320 spectrum consists of two absorption maxima, one at
electron microscope. The films were mounted on the sample around 330 nm and another at around 630 nm, which
studs by means of double-sided adhesive tapes and were
are attributable to the π-π* transition of the benzenoid
shadowed with gold prior to SEM measurements. The SEM
measurements were performed at an accelerating voltage of rings and the absorption of the quinoid rings, respec-
10 kV. tively.23 Further studies revealed that the benzenoid
absorption peak for the mPEG-g-PANi samples exhibits
Results and Discussion a blue shift and the shift increases with the graft
concentration. The phenomenon indicates that the non-
Synthesis of the mPEG-g-PANi Copolymers. The planar conformation of the PANi backbone, which leads
processes for the synthesis of the mPEG-g-PANi copoly- to a decrease in effective conjugate length, is increased
mer are shown schematically in Figure 1. The composi-
tions of the mPEG-g-PANi samples, prepared under (21) Tang, J.; Jing, X.; Wang, B.; Wang, F. Synth. Met. 1988, 24,
different feed ratios of mPEGCl to aniline in LM, are 231.
summarized in Table 1. The graft concentration and (22) Barbero, C.; Miras, M. C.; Haas, O.; Kötz, R. O. J. Electroanal.
Chem. 1993, 55, 3591.
volume and weight fractions of the grafted mPEG in the (23) Pouget, J. P.; Józefowicz, M. E.; Epstein, A. J.; Tang, X.;
copolymer are calculated from elemental analysis. Thus, MacDiarmid, A. G. Macromolecules 1991, 24, 779.
584 Chem. Mater., Vol. 13, No. 2, 2001 Wang et al.

Table 1. Compositions of the mPEG-g-PANi Copolymers

feed mol C/N mol graft vol frac. of wt frac. of wt frac. of surf. graft vol frac. of
polymers ratioa ratiob concnc mPEG (%)b,d mPEG (%)b mPEG (%)e concnf,g mPEG (%)d,f
polyaniline 5.96 0 0 0 0 0
mPEG-g-PANi#1 1:20 7.09 0.012 28.4 20.9 23 0.01 23
mPEG-g-PANi#2 1:10 8.12 0.023 43.4 33.8 33 0.02 37
mPEG-g-PANi#3 1:8 9.26 0.035 54.2 44.1 43 0.03 51
mPEG-g-PANi#4 1:6 10.3 0.046 61.1 50.3 54 0.04 58
mPEG-g-PANi#5 1:1.5 37.1 0.257 91.8 88.3 85 h h

a Ratio of mPEGCl per aniline unit. b Determined by elemental analysis. c Defined as the number of mPEG units (MW ∼2000) per

aniline unit of PANi. It is determined from the C/N molar ratio of each copolymer, taking into account that the C/N molar ratio for PANi
is 6 and there are about 90 carbons per mPEG chain. Thus, the graft concentration is calculated from the expression ([C/N] - 6)/(84 +
[C/N]). d Based on the experimentally determined density for the lightly cross-linked PANi film ) 1.5 g/cm3 and the density of mPEG )
1.0 g/cm3 specified in the Aldrich catalog. e From TG analysis. f From XPS analysis. g Determined from the XPS-derived CO component
and N1s spectral areas using the expression ([CO]/90)/[N]. h mPEG-g-PANi#5 cannot be cast into a free-standing film, due to the high
content of grafted mPEG.

Figure 2. FT-IR spectra of (a) the pristine LM base powder,

(b) the pristine EM base powder, and (c) the mPEG-g-PANi#4
powder (graft concn ) 0.046).

upon the incorporation of the flexible mPEG side Figure 3. UV-visible absorption spectra of NMP solutions
chains.24 The UV-visible absorption spectrum of an of (a) the pristine LM base, (b) the pristine EM base, (c) the
aqueous solution of the mPEG-g-PANi sample with a mPEG-g-PANi#2 (graft concn ) 0.023), (d) the mPEG-g-
graft concentration of 0.257 is also shown in Figure 3f. PANi#4 (graft concn ) 0.046), (e) the mPEG-g-PANi#5 (graft
It can be seen that both of the absorption maxima at concn ) 0.257), and an aqueous solution of (f) the mPEG-g-
PANi#5 (graft concn ) 0.257).
314 and 601 nm exhibit even more remarkable blue
shifts in an aqueous solution when compared to those for the copolymer samples. The onset of the first major
observed in the NMP solution. This phenomenon may weight loss at about 280 °C corresponds to the decom-
be due to the hydrogen-bonding effect of NMP25 which position of the grafted mPEG side chains. The second
promotes a thermodynamically more stable PANi chain major weight loss begins at about 500 °C, corresponding
conformation and restricts the polymer to lower energy, to the decomposition of the PANi backbone in the EM
higher-planarity states. Alternatively, the decrease in state.26 For each copolymer, the weight fraction of the
the effective conjugation length of the PANi backbone mPEG side chains derived from the first major weight
becomes more drastic in the presence of strong polar loss step in the TG analysis curve is also shown in Table
group interactions between the mPEG side chain and 1. In each case, the percent weight loss coincides
the aqueous medium.7 approximately with the weight fraction of mPEG in the
Thermal Analysis. The mPEG-g-PANi copolymers copolymer determined from the elemental analysis
are also subjected to TG analysis. Figure 4 shows the results. The decomposition of the PANi backbone is
respective TG analysis curves of the pristine EM base, affected by the grafted mPEG chains only at high
the mPEG-g-PANi copolymers of graft concentrations extents of grafting. For sample with a high graft
of 0.012, 0.023, 0.035, 0.046, and 0.257, and the pristine concentration of 0.257, the onset temperature for the
mPEG. The mPEG-g-PANi samples (curves 2-6) show second major weight loss is reduced to about 420 °C.
intermediate weight loss behavior in comparison to that Obviously, the tertiary aromatic amines substituted by
of the mPEG (curves 7) and that of the EM base (curves alkyl groups are thermally less stable than the second-
1). A distinct two-step degradation process is discernible ary amines.10

(24) Moon, H. S.; Park, J. K. Macromolecules 1998, 31, 6461. (26) Kang, E. T.; Neoh, K. G.; Tan, T. C.; Khor, S. H.; Tan, K. L.
(25) Chen, S. A.; Lee, H. T. Macromolecules 1993, 26, 3254. Macromolecules 1990, 23, 2918.
Poly(ethylene glycol)-Grafted Polyaniline Chem. Mater., Vol. 13, No. 2, 2001 585

Figure 4. TG analysis curves of (1) the pristine EM base, (2) Figure 5. Effect of the mPEG graft concentration on the
the mPEG-g-PANi#1 (graft concn ) 0.012), (3) the mPEG-g- conductivity of the 1 M HClO4-protonated mPEG-g-PANi films.
PANi#2 (graft concn ) 0.023), (4) the mPEG-g-PANi#3 (graft (The point at 0 graft concn corresponds to that of the proton-
concn ) 0.035), (5) the mPEG-g-PANi#4 (graft concn ) 0.046), ated EM homopolymer.)
(6) the mPEG-g-PANi#5 (graft concn ) 0.257), and (7) the
mPEG sample.

Table 2. Solubility of Polyaniline and mPEG-g-PANi

Samples
solventsa
polymersb NMP DMSO THF CHCl3 CH2Cl2 water
EM base S SS SS SS I I
mPEG S S S S S S
mPEGCl S S S S S S
mPEG-g-PANi#1 S SS SS SS I I
mPEG-g-PANi#2 S SS SS SS I I
mPEG-g-PANi#3 S P P P P I
mPEG-g-PANi#4 S S S S S I
mPEG-g-PANi#5 S S S S S S
a Key: S, soluble (up to a concn of at least 1 g/100 mL); SS,

slightly soluble; P, partially soluble; and I, insoluble. b The graft

concentrations for the mPEG-g-PANi copolymers correspond to
those of Table 1. Figure 6. UV-visible absorption spectra of HClO4-protonated
coatings of (a) the pristine EM base, (b) the mPEG-g-PANi#2
Solubility of the mPEG-g-PANi Samples. The (graft concn ) 0.023), (c) the mPEG-g-PANi#3 (graft concn )
0.035), and (d) the mPEG-g-PANi#4 (graft concn ) 0.046) on
mPEG-g-PANi samples with graft concentration greater
quartz substrates.
than 0.035 are readily soluble in common organic
solvents, such as NMP, CHCl3, THF, and DMSO. Poly- substituted mPEG chains can also alter the conforma-
(ethylene glycol) is well-known for its excellent solubility tion of the PANi chain. The bulky side chains can induce
in both polar and nonpolar solvent.12 The mPEG-g-PANi nonplanar conformations, which in turn can cause a
solutions with a concentration up to 1.0 g/100 mL are decrease in the effective conjugation length of the PANi
stable under ambient condition for months without backbone. In this way, the bulky side chain destabilizes
precipitation. For the mPEG-g-PANi sample with a the polysemiquinone radical cation and gives rise to
graft concentration of 0.257 and above, it is also soluble higher redox potentials. Similar phenomenon has been
in water with a solubility up to 1.0 g/100 mL. The reported in the literature for the substituted PANi
solubility results are summarized in Table 2. derivatives.27 Nevertheless, the nearly linear depend-
Electrical Conductivity of the Doped mPEG-g- ence of bulk conductivity on the volume fraction of
PANi Film. Figure 5 shows the dependence of the mPEG in the copolymer suggests that the conforma-
electrical conductivity of the 1 M HClO4-protonated tional effect is of less importance.
mPEG-g-PANi copolymer film as a function of the Figure 6 shows the UV-visible absorption spectra of
volume fraction of mPEG in the graft copolymer. The the HClO4-protonated polyaniline and the mPEG-g-
bulk conductivity of the HClO4-protonated copolymer PANi coatings on quartz plates. Solutions (1 wt % NMP)
exhibits an approximately linear decrease with the of the respective copolymers were used for film casting
increase in volume fraction of mPEG in the copolymer. on quartz plates. As in the case of all the other free-
The reduction in conductivity can be explained by the standing films cast from the copolymer solutions (see
volumetric “diluting effect” of the grafted mPEG chains. Experimental Section), the cast films on quartz plates
The intermolecular steric effect introduced by the bulky were also heated in a constant temperature oven at 110
mPEG side chains will have a diluting effect on the °C for 2 h to form a lightly cross-linked coating on each
PANi chains and will thus contribute to the reduction
in conductivity of the mPEG-g-PANi sample. The N- (27) Leclerc, M.; Daprano, G.; Zotti, G. Synth. Met. 1993, 55, 231.
586 Chem. Mater., Vol. 13, No. 2, 2001 Wang et al.

Figure 7. XPS N1s core-level spectra of neutral and HClO4-protonated films of (a, d) the EM, (b, e) the mPEG-g-PANi#2 (graft
concn ) 0.023), and (c, f) the mPEG-g-PANi#4 (graft concn ) 0.046). The corresponding C1s core-level and wide-scan spectra of
(g, j) the EM base, (h, k) the mPEG-g-PANi#2 base, and (i, l) the mPEG-g-PANi#4 base are also shown.

quartz substrate. The UV-visible absorption spectrum Thus, the protonation-deprotonation behavior of the
of the doped polyaniline shows a characteristic polaron PANi chains in the mPEG-g-PANi copolymer is not
peak at 430 nm and a localized polaron absorption peak unlike that of the homopolymer of the EM base.
at 800 nm, together with a less well defined π-π* Figure 7g-l shows the corresponding C1s core-level
transition band at around 320 nm.28 For the mPEG-g- and wide-scan spectra of the three films before proton-
PANi sample with a low graft concentration (∼0.023) ation. In the case of the pristine EM base film, the C1s
of mPEG, the characteristic of UV-visible absorption core-level spectra can be curve fitted with three peak
spectrum is similar to that of PANi. However, for the components, with the BE at 284.6 eV for the CH species
mPEG-g-PANi samples with higher graft concentra- from benzene rings, at 286.2 eV for the CO species, and
tions, the localized polaron absorption band shifted to at 287.7 eV for the CdO species.30 The appearance of
longer wavelengths of about 900-1000 nm. The result trace amounts of the CO and CdO species may be
indicates that the grafted mPEG chains interfere with attributed to surface oxidation of the film.4 In the case
the doping process and the polaron delocalization. of the mPEG-g-PANi samples, the C1s core-level spectra
Surface Characterization of the mPEG-g-PANi can be curve-fitted with three components which are
Films. The respective N1s core-level spectra of EM and similar to those found in the pristine EM base, except
two mPEG-g-PANi copolymers films before and after that the intensity of the CO species is substantially
protonation by 1 M HClO4 are shown in Figure 7a-f. enhanced in each case. The enhancement of the CO peak
These spectra are deconvoluted into the following peak component is consistent with the presence of the grafted
components:4,29 imine (-Nd) peak component with the mPEG side chain. The increase in surface oxygen
binding energy (BE) at 398.2 eV, amine (-NH-) peak content, as revealed by the corresponding wide-scan
component with the BE at 399.4 eV, and two positively spectra, is also consistent with the increase in the CO
charged nitrogen (N+) peak components with the BEs peak intensity and the mPEG graft concentration. The
above 400 eV, based on the fixed line width approach surface graft concentration, defined as the number of
in peak synthesis adapted in the present work. It can mPEG units per aniline unit of PANi and derived from
be seen that for the mPEG-g-PANi base samples, the the CO component and N1s spectral area ratio, is also
presence of approximately equal proportions of the shown in Table 1. Thus, a good agreement between the
imine and amine peak components is not unlike that of bulk and surface graft concentration is observed. This
the EM base of PANi. This result gives further support result also suggests that the grafted mPEG units are
to the conclusion that the original LM backbone has distributed uniformly on all the PANi chains.
been oxidized to the EM state during the graft co-
Figure 8 shows the dependence of the cosine of water
polymerization process. Protonation of the mPEG-g-
contact angle of the mPEG-g-PANi film on the surface
PANi base samples results in the disappearance of the
and bulk volume fractions of mPEG in the copolymer.
imine component and the appearance of a corresponding
The surface volume fraction was determined from the
proportion of the positively charged nitrogen. This
XPS-derived surface graft concentration (see Table 1).
phenomenon is consistent with the fact that protonation
To a good approximation, the cosine of the contact angle
of the EM base occurs preferably at the imine units.4,5
varies linearly with both the surface and the bulk
(28) Cao, Y.; Smith, P.; Heeger, A. J. Synth. Met. 1989, 32, 263.
(29) Tan, K. L.; Tan, B. T. G.; Kang, E. T.; Neoh, K. G. Phys. Rev. (30) Briggs, D. In Surface Analysis of Polymers by XPS and Static
B 1989, 39, 8070. SIMS; Cambridge University Press: Cambridge, U.K., 1998; p 65.
Poly(ethylene glycol)-Grafted Polyaniline Chem. Mater., Vol. 13, No. 2, 2001 587

Figure 8. Dependence of the cosine of water contact angle Figure 9. SEM images of the platelets adhered on (a) the
(q) of the mPEG-g-PANi film on the surface and bulk volume pristine PANi (EM base) film surface, (b) the mPEG-g-PANi#1
fractions of mPEG in the copolymer. film surface (graft concn ) 0.012), (c) the mPEG-g-PANi#3 film
surface (graft concn ) 0.035), and (d) the mPEG-g-PANi#4 film
volume fractions of the hydrophilic mPEG chains. By surface (graft concn ) 0.046).
the Cassie relationship,31 the wetting data have, thus, erty of PEG is believed to have resulted from its
provided a surface measurement that mirrors the bulk. minimum interfacial free energy in water, its hydro-
The contact angle data also suggest that the graft philicity, its high surface mobility, and its steric stabi-
copolymer films have a rather homogeneous microstruc- lization effects, as well as its unique solution properties
ture.32 and molecular conformation in water.12 The PEG mol-
Platelet Adhesion. For the platelet adhesion stud- ecule has a large excluded volume in water. In an
ies, PRP separated from the blood of a healthy dog was aqueous environment, a surface with hydrated flexible
incubated on the pristine PANi and mPEG-g-PANi base PEG chains and a large excluded volume tends to repel
film surfaces, and the extents of platelet adhesion on protein molecules that approach it. In the absence of
the surfaces were observed by SEM. Figure 9a-d shows protein adsorption, the platelet adhesion is suppressed.34
the respective SEM images of the platelets adhered to
the pristine EM base surface and three mPEG-g-PANi Conclusion
base film surfaces of different graft concentrations. It
can be seen that the amount of platelet adhesion A new copolymer, methoxy poly(ethylene glycol)-
decreases with increasing mPEG graft concentration in grafted polyaniline, or mPEG-g-PANi, was successfully
the copolymer film. The mPEG-g-PANi film with a graft synthesized by incorporating the chlorine end-capped
concentration of 0.046 is very effective in preventing derivative of methoxy PEG (MW ∼2000) onto PANi
platelet adhesion. The result thus suggests that the through the N-alkylation of the leucoemeraldine form
mPEG-PANi film cast from the copolymer sample with of the PANi. The mPEG-g-PANi copolymers exhibited
a moderate mPEG graft concentration (bulk) of 0.046 enhanced solubility in common organic solvents with
can exhibit nonfouling surface properties. only a moderate reduction in their electrical conductiv-
PEG-containing polymers are commonly used as ity. For the mPEG-g-PANi sample with a graft concen-
blood-compatible materials.12 The PEG component is tration of 0.257, it also exhibited a solubility of up to
well-known for its ability to minimize blood protein 1.0 g/100 mL in water. The mPEG-g-PANi copolymer
adsorption onto the surface. The blood protein adsorp- with a mPEG graft concentration ([mPEG]/[aniline])
tion is the first step in the thrombosis process. The above about 0.05 exhibited good resistance toward
second step of the thrombosis involves the platelet platelet adhesion, suggesting that the graft-modified
adhesion. Usually, the platelet adhesion will not occur electroactive polymer had been imparted with a non-
to a significant extent if the blood protein cannot be fouling, blood-compatible surface.
adsorbed onto the surface.33 The protein-repelling prop- CM000829C

(31) Cassie, A. B. D. Discuss. Faraday Soc. 1952, 75, 5041. (33) Norde, W. Adv. Colloid Interface Sci. 1986, 25, 267.
(32) Drelich, J.; Wilbur, J. L.; Miller, J. D.; Whitesides, G. M. (34) Kjellander, R.; Florin, E. J. Chem. Soc., Faraday Trans. I 1981,
Langmuir 1996, 12, 1913. 77, 2053.