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Phosphorus, Sulfur, and Silicon and the

Related Elements
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Synthesis of Hybrid Nanocomposites

Based on Polyhedral Oligomeric
Silsesquioxane Using Atom Transfer
Radical Polymerization
a

Xiang-Mei Ma , Xue-Ying Liu , Bin Wang , Jia-Ju Ma , Ming-Xu Zhang

& Jie He

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Department of Chemical Engineering, Anhui University of Science

and Technology, Huainan, 232001 Anhui, P. R. China
b

Department of Chemical Engineering, Anhui Vocational & Technical

College of Industry and Trade, Huainan, 232007 Anhui, P. R. China
Accepted author version posted online: 18 Jun 2014.Published
online: 06 Jan 2015.

To cite this article: Xiang-Mei Ma, Xue-Ying Liu, Bin Wang, Jia-Ju Ma, Ming-Xu Zhang & Jie He (2015)
Synthesis of Hybrid Nanocomposites Based on Polyhedral Oligomeric Silsesquioxane Using Atom
Transfer Radical Polymerization, Phosphorus, Sulfur, and Silicon and the Related Elements, 190:2,
200-207, DOI: 10.1080/10426507.2014.914934
To link to this article: http://dx.doi.org/10.1080/10426507.2014.914934

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Phosphorus, Sulfur, and Silicon, 190:200207, 2015

C Taylor & Francis Group, LLC
Copyright 
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2014.914934

SYNTHESIS OF HYBRID NANOCOMPOSITES BASED ON

POLYHEDRAL OLIGOMERIC SILSESQUIOXANE USING
ATOM TRANSFER RADICAL POLYMERIZATION
Xiang-Mei Ma,1 Xue-Ying Liu,2 Bin Wang,1 Jia-Ju Ma,1
Ming-Xu Zhang,1 and Jie He1
Downloaded by [Orta Dogu Teknik Universitesi] at 10:50 11 June 2015

Department of Chemical Engineering, Anhui University of Science and

Technology, Huainan, 232001 Anhui, P. R. China
2
Department of Chemical Engineering, Anhui Vocational & Technical College of
Industry and Trade, Huainan, 232007 Anhui, P. R. China
GRAPHICAL ABSTRACT

POSS (CH2)3 Cl + CH2

POSS (CH2)3Cl

(R

CH2CH2CH2Cl )

CH3
C
C O
O
CH3

CuCl/bpy
110

oC

Si O Si
O
O
Si O Si
O
O
O
O
Si O Si
O
O
Si O Si

R
Si O Si CHCH
2CH2Cl
2
O
O
R Si O Si
O
RO
O
R O
Si O Si R
O
O
Si O Si
R
R
CH3
(CH2)3 CH2 [ C ]nCl
COOCH3

Abstract A new organic/inorganic hybrid polymer POSS/PMMA was prepared by atom transfer radical polymerization (ATRP), in which Octa( -chloropropyl) polyhedral oligomeric
silsesquioxane (POSSCl) was used as a crosslink agent to incorporate poly(methyl methacrylate) (MMA). The structure and composition of the composite was characterized using various techniques, including Fourier transform infrared spectroscopy (FTIR), 1H NMR, X-ray
diffraction (XRD) as well as gel permeation chromatography (GPC). All the results indicated that POSS molecule was successfully incorporated into the PMMA matrix. The thermal
stability property of the composite was investigated by thermal gravimetric analysis (TGA).

Received 27 December 2013; accepted 10 April 2014.

Address correspondence to Bin Wang, Department of Chemical Engineering, Anhui University of Science
and Technology, Huainan, 232001 Anhui, P. R. China. E-mail: wbmxmwzc@126.com
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gpss.
200

SYNTHESIS OF HYBRID NANOCOMPOSITES

201

The results showed that the composite displayed good thermal stability and higher temperatures
at maximum weight loss rate (Tmax ) than that of the pure PMMA homopolymer, which may be
attributed to the incorporation of rigid silica cube.
Keywords Atom transfer radical; composite; methyl methacrylate (MMA); Polyhedral
Oligomeric Silsesquioxane (POSS); polymerization (ATRP)

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INTRODUCTION
Organicinorganic nanocomposite materials have been regarded as a new generation
of high performance and high functional materials since they combine both the advantages
of the inorganic materials and organic polymers.1 Therefore, organicinorganic nanocomposite materials have been widely explored and used in the fields such as mechanics,
sensors, catalyst, energy, optical, and electronic devices.2 So synthesis and preparation of
organicinorganic nanocomposite have attracted much attention in the field of polymer
science. Among a series of inorganic components, polyhedral oligomeric silsesquioxane
(POSS) was the most interesting one because of its well-defined nanostructures, which have
inorganic silica cores surrounded by organic functional groups.3,4 POSS can be easily incorporated into a polymer matrix by either physical blending or chemical reaction to obtain
novel polymer hybrids with enhanced thermal and flammability resistance properties.
POSS-containing polymers have been previously prepared by conventional radical
copolymerization, condensation polymerization,57 or ring-opening metathesis polymerization,810 and it is difficult to form well-defined POSS-containing polymers with predictable
molecular weights, various architectures, and narrow molecular weight distributions.11 In
order to understand the effect of POSS in a polymer matrix, it is necessary to synthesize a
well-defined POSS-containing polymer. In recent years, atom transfer radical polymerization (ATRP) has been proved to be an efficient method to synthesize well-defined polymers,
which has been widely applied in the preparation of POSS-containing hybrid polymers with
well-defined topological structure.12 Matyjaszewski et al. reported the atom transfer radical polymerization of methacrylate functional POSS, and then using this method, block
copolymers and star-block copolymers were also prepared.13 Bai et al. firstly synthesized
POSS-containing ATRP initiator (POSS-PBI-Br) in three steps, and then ATRP of NIPAM
was carried out using POSS-PBI-Br as the initiator in the presence of CuBr/Me6 TREN.
Finally, the optical properties of POSS-containing hybrid polymer were investigated.14
Fei et al. synthesized a POSS/PMMA composite using Si Cl bond on monofunctional
POSS as an ATRP initiator, and the mono-dispersion of POSS in PMMA matrix was
achieved.15
Poly (methyl methacrylate) (PMMA) is an important thermoplastic material, which
presents interesting characteristics such as high transparency, high strength, and dimensional stability. However, its poor heat resistance limits its applications.16 Compared
with pure PMMA, POSS/PMMA exhibits unique thermal stability. For example, Weickmann et al. synthesized PMMA/POSS composites via the self-assembly of nonreactive [Si7 O9 (cyclohexyl)7 (OSiMeH)3 ] and [Si8 O12 (OSiMe2 H)8 ].17 Toepfer prepared crosslinked methacryloxypropyl POSS/PMMA nanocomposites by copolymerization.18 Zhao
et al. prepared octavinyl-POSS (OV-POSS)/ PMMA nanocomposites.19 In this article, we
prepared a star-shaped POSS/PMMA hybrid polymer using octa( -chloropropyl) polyhedral oligomeric silsesquioxane as the initiator in the presence of Bpy and CuCl, and the
chemical structure of the POSS/PMMA hybrid polymer was fully established by FT-IR,

202

X.-M. MA ET AL.

Si O Si
O
O
Si O Si
O
O
O
O
Si O Si
O
O
Si O Si

CH3
(CH2)3 CH2 [ C ]nCl
COOCH3

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Scheme 1 Molecular structure of POSS-PMMA.

1

H NMR, XRD, and GPC. The thermal properties of the hybrid polymer were also investigated by TGA.
RESULTS AND DISCUSSION
The POSS/PMMA hybrid polymer was synthesized by ATRP using octafunctional
POSS as the initiator in the presence of Bpy and CuCl. The chemical structure of the
hybrid polymer was first characterized by FT-IR (Figure 1). In the FT-IR spectrum of POSS
(Figure 1(A)), there is a strong absorption band at 1115 cm1, which is attributed to the
stretching vibration of Si O Si in the POSS molecule. The peak at 698 cm1 is due to

Figure 1 FT-IR spectra of POSS (A) and POSS/PMMA (B).

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SYNTHESIS OF HYBRID NANOCOMPOSITES

203

Figure 2 1H NMR spectra of POSS (A) and POSS/PMMA (B).

C Cl stretching. After the polymerization of MMA, some new absorption bands at 1732
and 1147 cm1 appear in the FT-IR spectrum of POSS/PMMA (Figure 1(B)) corresponding
to the carbonyl stretching vibration and C O C stretching vibration, respectively.20 The
absorption band of Si O Si stretching vibration is overlapped with the one of C O C
stretching vibration. Compared to the FT-IR spectrum of POSS, the peak at 698 cm1
disappears, which confirms that the ATRP of MMA was achieved using POSS as the
initiator.
In order to further confirm the structure of the POSS/PMMA composite, 1H NMR
spectra of POSS and POSS/PMMA are shown in Figure 2 For pure POSS, the signals at 0.83,
1.83, and 3.55 ppm were assigned to the protons in the -chloropropyl For POSS/PMMA,
the signal at 3.60 ppm is attributed to the protons in COOCH 3 , and the signals at
1.292.20 ppm and 0.701.24 ppm are assigned to the protons of methylene and methyl
in the backbone of PMMA.21 The signal of the proton in CH2 CH2 CH 2 Cl at 3.55 ppm

Figure 3 GPC curve of POSS/PMMA hybrid polymer.

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X.-M. MA ET AL.

Figure 4 XRD spectra of POSS (A) and POSS/PMMA (B).

Figure 5 TGA (5a) and DTG (5b) curves of PMMA (A) and POSS/PMMA (B and C).

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SYNTHESIS OF HYBRID NANOCOMPOSITES

205

disappeared in the 1H NMR of POSS/PMMA composite, so we draw the conclusion that

POSS/PMMA hybrid polymer was successful synthesized by ATRP.
Figure 3 shows the GPC curve of POSS/PMMA composite. The obtained
weight-average (M w ) and number-average (M n ) molecular weights from GPC analysis
were 809,800 and 1,249,800 g/mol, respectively. The molecular weight distribution of
POSS/PMMA is 1.54, which suggests that the polymerization of MMA was well controlled
using POSS as the initiator in the presence of Bpy and CuCl.
Figure 4 shows the XRD spectra of pure POSS (A) and POSS/PMMA composite (B).
From Figure 4(A), there are peaks at 2 = 7.3 , 9.1 , 12.0 , 21.8 , and 23.0 , indicating
the crystal structure of pure POSS.22,23 However, after the polymerization, these peaks
disappeared in the XRD spectrum of POSS/PMMA polymer in Figure 4(B). So the POSS
molecule was dispersed evenly into the PMMA matrix by ATRP.
TGA curves of POSS/PMMA composite (POSS content is 5 wt% and 10 wt%,
respectively) and pure PMMA are shown in Figure 5(a). The thermal stability is improved
upon introduction of POSS into PMMA matrix. PMMA started sharp mass loss at about
231 C; However, POSS/PMMA were almost no mass loss before 250 C. The values of
T d,10% T d,90% were found to increase with the increase of POSS. It was contributed to the
network formed by the reaction between PMMA and POSS.24 As shown in Figure 5(b),
POSS/PMMA nanocomposites exhibit higher temperatures at maximum weight loss rate
(T max ) compared with pure PMMA. For example, the T max of POSS/PMMA composite
containing 10% POSS is 41 C higher than that of pure PMMA with T max at 309 C. In
the case of POSS/PMMA nanocomposites, it is suggested that the Si O Si framework
and the steric hindrance effect of POSS can contribute to an improvement in the thermal
stability.25 So, the DTG analysis confirms that the POSS molecule was chemically bonded
to PMMA matrix through ATRP.

CONCLUSIONS
In this work, a new POSS/PMMA composite was successfully prepared using octa( chloropropyl) POSS as the initiator. The chemical structure of POSS/PMMA composite
were characterized by FTIR, 1H NMR, XRD, and GPC. The results show that POSS
molecule was successfully bonded to PMMA matrix and the polymerization was well
controlled. The data of TGA analysis suggest that the thermal stability of pure PMMA is
enhanced after the incorporation of the rigid POSS molecule, and the enhancement in the
thermal properties largely depended on the POSS content.

EXPERIMENTAL
Materials and Methods
Methyl methacrylate (MMA) was washed successively with 5% NaOH and then
washed with water until neutralization. After drying with anhydrous Na2 SO4 , MMA was
subsequently distilled under reduce pressure. 2,2 -bipyridine (Bpy) (AR) was purified and
prepared according to previously reported procedures.26 (3-Chloropropyl)trimethoxy silane
[ClC3 H6 Si(OCH3 )3] and other reagents were obtained from Shanghai Sinopharm Chemical
Reagents Co Ltd. without further purification.

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Synthesis of POSS/PMMA

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On the basis of related literature, POSSCI was synthesized.27 The polymerization

reactions were carried out under nitrogen using a vacuum-line system. POSSCl (0.10 g,
0.096 mmol), toluene (10 mL), MMA (10 mL, 94 mmol), CuCl (0.010 g, 0.10 mmol), and
Bpy (0.047 g, 0.30 mmol) were mixed in a polymerization tube. The tube was degassed
by three cycles of freezevacuumthaw and sealed by flame under vacuum. The tube was
immersed in an oil bath warmed at 110 C for 20 h and the solution turned reddish-brown.
After cooling down in the ice-water bath, the tube was opened and the mixture was diluted
with large amount of THF and filtrated. The filtrate was concentrated by rotary evaporator
followed by precipitation into a lot of methanol. The product was obtained after filtration
and dried in vacuum oven at 50 C (wt% yield: 35.2%).
Measurements
Fourier transform infrared spectroscopy (FT-IR) measurement was carried out on a
Bruker VECTOR-22 IR spectrometer, Each sample was formed into a KBr pellet for spectroscopic examination at room temperature. 1H NMR spectra were carried out on a Bruker
AVAN300 CE instrument using CDCl3 as the solvent and tetramethylsilane (TMS) as an
internal standard. The weight-average (M w ) and number-average (M n ) molecular weights
were measured on a Waters 515 gel permeation chromatograph (GPC) using polystyrene
as standards and THF (1.0 mL/min) as the elution. XRD spectra were collected on an
M18XHF-SPA X-ray diffraction instrument (MacScience Co. Japan). The thermogravimetric analyse (TGA) of samples were recorded on a Diamond TGA PerkinElmer High
Resolution Thermogravimetric Analyzer. The samples were heated with the heating rate of
10 C/min from room temperature to 600 C under a nitrogen atmosphere.
FUNDING
This work was supported by the National Basic Research Program of China under
Grant 973 Program (Grant No. 2012CB214900) and the National Science Foundation of
China (21271008).
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