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European Polymer Journal 41 (2005) 13261332

EUROPEAN
POLYMER
JOURNAL
www.elsevier.com/locate/europolj

Synthesis of well-dened, polymer-grafted silica nanoparticles


via reverse ATRP
Yun-Pu Wang *, Xiao-Wei Pei, Xiao-Yan He, Kun Yuan
Department of Chemistry, Gansu Key Laboratory of Polymer Materials, Institute of Polymer, Northwest Normal University,
Lanzhou 730070, PR China
Received 25 August 2004; received in revised form 11 December 2004; accepted 16 December 2004
Available online 30 January 2005

Abstract
The surface grafting onto ultrane silica via reverse ATRP of methyl methacrylate initiated by peroxide groups
introduced onto the surface and conventional ATRP of Styrene initiated by the hybrid nanoparticles were investigated.
The introduction of peroxide groups onto the silica surface was achieved by the reaction of hydrogen peroxide with
chlorosilyl groups, which were introduced by the treatment of silica with thionyl chloride. Well-dened polymer chains
were grown from the nanoparticle surfaces to yield individual particles composed of a silica core and a well-dened,
densely grafted outer polymer layer. The polymerization was closely controlled in solution at quite low temperature
such as 70 C. In both cases, linear kinetic plots, linear plots of molecular weight (Mn) versus conversion, in hydrodynamic diameter with increasing conversion, and narrow molecular weight distributions (Mw/Mn) for the grafted polymer samples were observed. Hydrolysis of silica cores by hydrouoric acid treatment enabled characterization of
cleaved polymer using GPC. Ultrathin lms of hybrid nanoparticles were examined using TEM and AFM.
2005 Elsevier Ltd. All rights reserved.
Keywords: Well-dened; Polymer-grafted; Silica; Reverse ATRP; Peroxide groups

1. Introduction
Grafting polymers onto solid surface is attracting
more and more interest due to their important applications ranging from colloidal stabilizers [1] to nanocomposite materials [2,3]. Known methods for grafting
polymer chains to particle surfaces entail chemisorption
of a reactive polymer end group to the surface [46],

Corresponding author. Tel.: +86 931 797 0686/8797; fax:


+86 931 797 0686/1989.
E-mail addresses: wangyp@nwnu.edu.cn, xiaoweipei1977@
163.com (Y.-P. Wang).

grafting a polymer chain through a monomer covalently


linked to the surface [710], or grafting a polymer chain
from a surface modied with polymerization initiators
[1113]. The so-called grafting from technique is commonly used to obtain covalently bound vinyl polymer by
conventional free radical polymerization chemistry in
conjunction with surface-bound initiators [14,15]. However, this approach cannot provide any good control
over the molecular weight, polydispersity, or terminal
chain functionality of the graft polymers. Furthermore,
a nonnegligible amount of soluble polymer is inevitably
formed during such synthesis. In principle, this problem
can be minimized by the use of more controlled/living
polymerization methods, because such methods aord

0014-3057/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2004.12.010

Y.-P. Wang et al. / European Polymer Journal 41 (2005) 13261332

Cl

Cl
Silica

SOCl2

Cl

Silica

Cl
Cl

ROO

Cl
Cl
Cl

R-OOH

ROO

ROO
ROO

CH3
R: CH3 C
CH3

OOR

Silica
OOR

OOR

1327

O
O
Reverse ATRP

Silica

OOR

Silica

ATRP

Fig. 1. Synthetic steps for forming hybrid copolymer-inorganic nanocomposite.

control over the molecular weight, polydispersity, and


structure of the resulting polymer [16]. In particular,
atom transfer radical polymerization (ATRP) [1719],
from surfaces has proven to be a versatile approach
for incorporating organic (co)polymers of precise molar
mass, composition, and functionality onto both planar
surface [2023], and colloidal/particulate substrates
[2432].
Considering the preparation of well-dened, polymer-grafted silica particles via reverse ATRP has been
much less reported yet. Herein, we reported that structurally well-dened, polymer-nanoparticle hybrids were
prepared by modifying the surface of ultrane silica with
peroxide groups for reverse atom transfer radical polymerization (ATRP). Fig. 1 shows the synthetic steps
for forming hybrid copolymer-inorganic nanocomposite. Polymerization using this nanoparticle initiator displayed the diagnostic criteria for a living/controlled
radical polymerization.

180 m2/g and a mean particle diameter of 16 nm, it


was kept at 120 C in vacuum for 36 h prior to use. Tetrahydrofuran (THF), benzene and dioxane (AR, Shanghai No. 1 Chemical Reagent Factory) were reuxed over
sodium and distilled twice before use. All other regents
were used without further purication.
2.2. Chlorination of silanol groups with thionyl chloride
The chlorination of silanol groups on silica particle
was carried out according to a modied literature procedure [34]. Ultrane silica (6.0 g) was added into a dry
250 ml round-bottom ask equipped with a reux condenser and a magnetic stirrer. Thionyl chloride (50 ml)
was charged followed by the addition of 50 ml benzene.
The mixture was stirred and reuxed for 50 h. After the
reaction, unreacted thionyl chloride and benzene were
removed by distillation and dried at 90 C in vacuum
for 24 h. The treated silica was stored in a desiccator
in vacuum.

2. Experimental
2.3. Introduction of peroxide groups onto silica surface
2.1. Materials
Methyl methacrylate (MMA), and styrene (St) (AR,
Shanghai Chemical Reagent Plant) were washed with
5% NaOH and ion-free water, stirred over CaH2 overnight, and distilled before use. CuCl2 6H2O was dehydrated by the reactions with thionyl chloride [33].
CuCl was puried by stirring in acetic acid, ltered
and washed with ethanol and dried. 2,2 0 -Bipyridine
(bipy) was recrystallized from acetone. The ultrane silica (Zhoushan Mingri Nanometer Material Co., Ltd.,
China) used in this study has a specic surface area of

The introduction of peroxide groups onto ultrane


silica was achieved by the reaction of chlorosilyl groups
on the surface with tert-butyl hydroperoxide (TBHP) in
the presence of sodium bicarbonate as dehydrohalogenation catalyst. A general procedure is as follows: The
treated ultrane silica (3.0 g) was added into a dry
100 ml round-bottom ask equipped with a magnetic
stirrer. Then dioxane (45 ml), TBHP (6 ml) were charged
followed by the addition of 0.15 g sodium bicarbonate.
The mixture was stirred under nitrogen at 20 C in the
dark for 12 h. After the reaction, resulting ultrane silica

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Y.-P. Wang et al. / European Polymer Journal 41 (2005) 13261332

was washed with methanol three times and dried at


20 C in vacuum for 24 h [35].
2.3.1. Determination of chlorosilyl groups on silica surface
The ultrane silica having chlorosilyl groups (0.2 g)
and sodium bicarbonate (0.01 g) were charged into a
dry 100 ml ask followed by the addition of 25 ml distilled water. Then hydrogen chloride formed by the
hydrolysis of chlorosilyl groups was titrated with
0.1 mol/l of silver nitrate solution using potassium chromate solution as indicator [36]. The chlorosilyl groups
introduced onto silica surface were determined to be
0.30 mmol/g.
2.3.2. Determination of peroxide groups on silica surface
The ultrane silica having peroxide groups (0.2 g)
and acetic anhydride (10 ml) were charged into a dry
50 ml ask followed by the addition of 0.5 g potassium
iodide, and the mixture was stirred for 20 min. Then isolated iodide was titrated with 0.1 mol/l sodium hyposulte using starch as an indicator [37]. The content of
peroxide groups introduced onto the ultrane silica surface was determined to be 0.08 mmol/g.
2.4. General procedure for the reverse ATRP of MMA
Ultrane silica having peroxide groups (0.46 g) and
16 ml cyclohexanone were charged into a 50 ml dry ask
equipped with a magnetic stirrer. The mixture was ultrasonicated while stirring for 30 min. Then 0.051 g of
CuCl2 and 0.115 g of bipy were added into this ask.
The ask was subsequently evacuated and ushed with
nitrogen three times. Then degassed monomer: MMA
8 ml was injected and the solution was further degassed
by three freezepumpthaw cycles. The mixture was stirred rapidly under nitrogen and placed in a thermostatically controlled oil bath at the reaction temperature
70 C. After a certain time, the viscous mixture was diluted with THF and the polymer-grafted silica nanocomposite was separated by centrifugation. Several
washings of the PMMA modied silica with THF were
done to remove ungrafted PMMA. The product was isolated by precipitation in a large excess of methanol and
dried at 50 C in vacuum for 24 h.
2.5. Synthesis of block copolymer-grafted hybrid
nanocomposite
Hybrid nanocomposite possessing PMMA-b-PSt
copolymer was prepared using the same general procedure as described previously, except with SiO2-g-PMMA
hybrid nanoparticles as macroinitiator to proceed block
copolymerization reaction with styrene in the presence
of CuCl/bipy catalyst via a conventional ATRP process.
A general procedure is as follows: SiO2-g-PMMA hybrid
nanoparticles (0.575 g) and 5 ml cyclohexanone were

charged into a 25 ml dry ask equipped with a reux


condenser and a magnetic stirrer. The ask was ultrasonicated while stirring for 30 min. After dissolution of the
solids, CuCl (0.009 g) and bipy (0.041 g) were added to
this ask while the mixture was in the frozen state.
The ask was subsequently evacuated and ushed with
nitrogen three times. Then degassed monomer: Styrene
2 ml was injected and the solution was further degassed
by three freezepumpthaw cycles. The mixture was stirred rapidly under nitrogen and placed in a 110 C oil
bath. Samples were taken periodically via syringe for kinetic analysis of the polymerization. After some time,
the viscous mixture was then diluted with THF and
the copolymer-grafted silica nanoparticles were separated by centrifugation. Several washings of the copolymer modied silica with THF were done to remove
ungrafted PSt. The product was isolated by precipitation
in a large excess of methanol, washed 23 times with
pure methanol and distilled water respectively, which removed virtually all the remaining Cu-salts. Then the
white mass obtained was dried at 50 C in vacuum for
24 h.
2.6. General procedure for cleavage of (co)polymers
from hybrid nanoparticles
As for the grafts of SiO2-g-PMMA hybrid nanoparticles and SiO2-g-(PMMA-b-PSt) hybrid nanoparticles
were detached from the silica surface via transesterication as described in [31]. SiO2-g-PMMA hybrid nanoparticles (100.0 mg) were dissolved in 1 ml of toluene,
along with Aliquat 336 (phase transfer catalyst,
10.0 mg). A 49% HF (aq) solution (1 ml) was added to
the particle solution, and the reaction was allowed to stir
at room temperature overnight. PMMA was recovered
by precipitation into methanol and vacuum ltration
through ne grain glass frit, yielding a white powder.
Similar procedure was followed for the cleavage of block
copolymer.
2.7. Characterization
FT-IR spectroscopy patterns were recorded on a Nicolet AVATAR 360 FT-IR system. Powder samples were
dispersed in a hydrous methylene chloride and drops of
the liquid were spread on KBr plates.
The microstructure of these hybrid nanocomposites
was imaged using a JEOL 1200 EX TEM. TEM samples
of nanoparticles were prepared by casting one drop of a
dilute colloid solution onto a carbon-coated copper grid.
AFM measurement was performed under ambient
condition using a SPI 38001 X scanning probe microscope system (Seiko Instruments Inc.) operated in tapping mode with standard 125 lm single-crystal silicon
cantilevers (nominal spring constant and resonance frequency respectively 50 N/m and 300 kHz).

Y.-P. Wang et al. / European Polymer Journal 41 (2005) 13261332

1329

Gel permeation chromatography (GPC) analysis of


the samples were performed at a ow rate of 0.80 ml/
min and 25 C in THF by using a Waters 150 component system (IR detectors) equipped with ultra-u-stragel
columns (10 nm and 1000 nm) after calibrated with standard polystyrene (PSt).

3. Results and discussion


Fig. 2 is the IR analysis of the untreated silica particles, PMMA-grafted hybrid nanocomposite and SiO2-g(PMMA-b-PSt) hybrid nanocomposite. In the IR spectra of PMMA-grafted hybrid nanocomposite, a new
adsorption peak at 1732 cm1, which is a characteristic
peak of the C@O present in PMMA. The adsorption
peak at 1091 cm1 results from SiO stretching of silica.
Moreover, the peak at 755 cm1 can be attributed to the
CCl stretching, indicating the presence of an activated
alkyl chlorine at the polymer chain end, which enables
ATRP to synthesis copolymer-grafted hybrid nanocomposite. In the IR spectra of SiO2-g-(PMMA-b-PSt) hybrid nanocomposite, the most interesting outcome is
the appearance of some adsorption peaks at 699 cm1
and 14001600 cm1, which are characteristic peaks of
PSt. On the other hand, the IR spectra of SiO2-g-

Fig. 2. FT-IR spectrum of (a) the untreated silica particles,


(b) PMMA-grafted hybrid nanocomposite and (c) SiO2g-(PMMA-b-PSt) hybrid nanocomposite.

Fig. 3. GPC traces of (a) the grafted PMMA and (b) the
grafted PMMA-b-PSt.

(PMMA-b-PSt) hybrid nanocomposite was the same as


that of PMMA-grafted hybrid nanocomposite. These results indicate that PMMA and PMMA-b-PSt are
grafted onto the surface of silica.
Information about the molecular weights and molecular weight distributions of the grafted PMMA and
PMMA-b-PSt were gained by etching the silica cores.
Fig. 3 shows GPC traces of the grafted PMMA and
PMMA-b-PSt. As shown in Fig. 3, the GPC curves
are all symmetric and unimodal, the narrow GPC curves

Fig. 4. First order kinetic plot and molecular weight versus


conversion plot for the reverse ATRP of MMA from silica
nanoparticles. Experimental conditions: temperature: 70 C,
[silica initiator]/[CuCl2]/[bipy]/[MMA] = 1:10:30:2000, cyclohexanone as the solvent.

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Y.-P. Wang et al. / European Polymer Journal 41 (2005) 13261332

indicate that the polymerization occurred in a controlled


manner.
Fig. 4 shows the rst order kinetic plot and molecular
weight versus conversion plot for the reverse ATRP of
MMA from silica nanoparticles. A straight line through
the origin is observed, indicating that the kinetics is rst
order in monomer and that the concentration of propagating radicals remains constant during the polymerization. The Mn GPC of PMMA (grafted) increase linearly
with the increase of conversion and the molecular weight
distributions are relatively narrow (<1.32). The above
results revealed that the graft polymerization of MMA
from silica surface via reverse ATRP is a living/controlled polymerization.
From the content of peroxide groups on silica surface, monomer conversion, and the molecular weight
(Mn) of detached chains, it is possible to calculate the
initiation eciency. For the reverse ATRP of MMA
from silica nanoparticles, the initiation eciencies were
low from the initial stages of the reactions. As the reaction proceeded, the molecular weight of cleaved PMMA
approached theoretical values, indicating that the initiation eciency also increased with reaction time. In the
case of MMA reverse ATRP from silica nanoparticles,
a gradual increase in the initiation eciency revealed
that new chains were continuously formed with longer
reaction times. Table 1 summarize the results of all polymerization under various experimental conditions.
The morphologies of functional silica particles, hybrid nanoparticles possessing tethered homopolymer of
PMMA and block copolymer PMMA-b-PSt were investigated using TEM (Fig. 5). Samples were prepared by
drop-casting dilute solutions of these nanoparticles onto
carbon-coated copper grids, followed by evaporation of
the solvent in air. TEM has provided extensive information about the sizes and, to a much lesser extent, the
shapes of silica nanoparticles. Fig. 5(a) revealed that
functional silica particles are well dispersed forming no

large aggregates and with an average eective diameter


(De) of 16 nm were obtained. Silica colloids with peroxide groups on the surface were used in the reverse ATRP
of MMA. Thus, we obtain much larger particles when
the functional silica particles as an initiator for subsequent growth of the polymeric shell. From the TEM
micrographs of these hybrid nanoparticles with dierent
polymer chain lengths, we can clearly see that the silica
nanoparticles are uniformly dispersed without forming
any aggregate. The average interparticle distance is
much larger than that of the functional silica nanoparticles and more importantly, it increases with increasing chain length of the graft polymer. As shown in
Fig. 5(b), the size of the PMMA-grafted hybrid nanoparticles range from 30 nm to 50 nm, averaging about
40 nm. Most of the PMMA-grafted hybrid nanoparticles appear to be roughly spherically symmetric,
although several of the larger nanoparticles appear to
be rather irregular in TEM images. From Fig. 5(c), we
can observe that much larger hybrid nanoparticles
(De  60 nm) are well dispersed. There is no doubt that
our synthetic method for preparing the initiator-coated
silica nanoparticles is eective to form brush surfaces,
which produce the large interparticle distances due to
the steric interaction force among the grafted particles.
This nding will give a new possibility to produce an array of silica nanoparticles with a controlled spacing in
polymer lm.
Tapping mode AFM was carried out to investigate
the surface topography of these hybrid nanocomposite
after Soxhlet extraction in THF for 24 h. Fig. 6 shows
a typical topography image of (a) the PMMA-grafted
hybrid nanocomposite and (b) SiO2-g-(PMMA-b-PSt)
hybrid nanocomposite. As shown in Fig. 6(a), bare particles formed loosely packed arrays, with clearly discernible individual nanoparticles. Protrusions are clearly
visible on height image. The protrusions were not detected on the functionalized silica wafer prior to poly-

Table 1
Experimental conditions and results for the reverse ATRP of MMA from silica nanoparticles and ATRP of St from PMMA-grafted
silica nanoparticles
Experiment

Colloidal initiator

Monomer

Conditionsd

1
2
3
4
5

Functional silica
Functional silica
Functional silica
SiO2-g-PMMAe
SiO2-g-PMMA

MMA
MMA
MMA
St
St

2000:1:10:30,
2000:1:10:30,
2000:1:10:30,
2000:1:10:30,
2000:1:10:30,

70 C
70 C
70 C
110 C
110 C

Reaction
time (h)

Conversiona (%)

Mn GPC

Mn th

PDIb

fc

2
8
24
16
24

2.1
4.5
11.3
3.7
6.1

18,283
28,548
44,367
64,742
65,483

4205
9011
22,627
36,255
41,254

1.31
1.19
1.18
1.41
1.39

0.23
0.32
0.51
0.56
0.63

Conversion values determined using gravimetric analysis.


PDI: Molecular weight distribution is calculated from Mw/Mn.
c
f: Initiation eciency calculated from f = Mn th/Mn GPC.
d
Conditions correspond to molar ratios of monomer, colloidal initiator, CuCl2 (or CuCl for experiment 4, 5), and bipy cyclohexanone as the solvent.
e
For the grafted PMMA (Mn = 28,548, Mw/Mn = 1.19).
b

Y.-P. Wang et al. / European Polymer Journal 41 (2005) 13261332

1331

Fig. 5. TEM of (a) functional silica particles, (b) PMMA-grafted hybrid nanocomposite and (c) SiO2-g-(PMMA-b-PSt) hybrid
nanocomposite.

Fig. 6. Tapping mode AFM images and three-dimensional height images of (a) the PMMA-grafted hybrid nanocomposite and (b)
SiO2-g-(PMMA-b-PSt) hybrid nanocomposite.

merization. The mean lm thickness of the PMMA layer


determined by AFM topography imaging in the vicinity
of the scratch was 10.0 1.0 nm. The mean diameter of
the protrusions determined by AFM is about 40 nm.

Prolonged Soxhlet extraction had no eect on the lm


thickness and surface topography, indicating that the
remaining PMMA is covalently linked to the silica wafer
and any loosely bound PMMA chains are completely

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Y.-P. Wang et al. / European Polymer Journal 41 (2005) 13261332

removed by the treatment. Meanwhile, some ungrafted


silica nanoparticles, which surfaces are relatively smooth
can also be observed. That because the silica nanoparticles arrayed densely prior to polymerization, so steric
crowding will prevent some polymer chains graft from
the silica surface. Fig. 6(b) depicts the AFM image of
PMMA-b-PSt copolymer brushes graft on silica particles. The section analysis of AFM images gives the mean
lm thickness of the PMMA-b-PSt copolymer layer in
the range of 2931 nm. The mean diameter of the
copolymer-grafted silica nanoparticles determined by
AFM is about 80 nm. Meanwhile in AFM image of
SiO2-g-(PMMA-b-PSt), the interparticle spacing was
considerably larger than for the PMMA-grafted silica
particles, presumably due to the higher DP of PSt in
the outer shell.

4. Conclusion
We present the rst report of structurally well-dened, polymer-grafted hybrid nanocomposites were prepared by introducing the surface of ultrane silica with
peroxide groups for reverse ATRP. Well-dened polymer chains were grown from the nanoparticle surfaces
to yield individual particles composed of a silica core
and a well-dened outer polymer layer. Polymerization
using this treated silica initiator displayed the diagnostic
criteria for a living/controlled radical polymerization.

Acknowledgment
This work was partly supported by a Natural Science
Foundation of China (No. 20074026).

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