Journal of Molecular Catalysis A: Chemical 363–364 (2012) 195–199

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Journal of Molecular Catalysis A: Chemical

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

4,4 -Bipyridine phosphotungtic salt: A recoverable versatile

photo-polymerization catalyst
Dianyu Chen ∗ , Xueying Wang, Gaowen Yang, Qiaoyun Li, Wen Chai, Rongxin Yuan, Shifan Liu,
Fei Gao, Hongyu Jin, Soumyajit Roy
Jiangsu Key Laboratory of Advanced Functional Materials, Department of Chemistry and Materials Engineering, Changshu Institute of Technology, Changshu 215500, PR China

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

Article history: 4,4 -Bipyridine phosphotungtic salt has been synthesized and used as a special catalyst for vinyl poly-
Received 3 June 2012 merization. This is a fast and smooth reaction, and high molecular weight polymers with narrow
Received in revised form 14 June 2012 polydispersity are obtained within 60 min. The compound was structurally characterized by elemen-
Accepted 16 June 2012
tal analysis, IR spectroscopy and 1 H NMR spectroscopy. The electrochemical property was determined
Available online 25 June 2012
on a CHI 660 electrochemistry workstation. The polymerization initiated by 4,4 -bipyridine phospho-
tungtic salt showed controlled characteristics, the catalyst can be isolated from polymer product easily
Keywords:
and reused for at least 10 times.
4,4 -Bipyridine phosphotungtic salt
Electrochemical © 2012 Elsevier B.V. All rights reserved.
Catalytic polymerization
Recoverable

1. Introduction by electrochemistry workstation. The catalysis activity was studied

in photo-polymerization of vinyl monomers.
Heteropolyoxometalates (HPMs) had attracted much attention
in recent years for the potential catalysis application [1–5]. HPMs
2. Experimental
had been found to be excellent catalysts for a number of chemical
reactions, e.g. hydration [6–11], alkylation [12–17], transesteri-
2.1. Materials and instruments
fication [18–21], Prins reaction [22–24], etc. However, the only
polymerization reaction initiated by HPMs, to date, was cycle-
All chemicals purchased were of reagent grade and used with-
opening polymerization of epoxy compounds such as epoxyethane,
out further purification. The elemental analyses for C, H and N were
epoxypropane, and tetrahydrofuran [25,26]. Our research group
performed with an EA1110-CHNS elemental analyser. The IR spec-
was the first to report the polymerization of styrene [27,28], which
tra were obtained on a NICOLET380 spectrum using KBr disks in the
was the only polymerization example for vinyl monomers.
range 4000–400 cm−1 . 1 H NMR spectra were recorded on a BRUKER
Styrene polymerization initiated by HPMs was excellent, and
Avance DPX300 MHz spectrum. Polymerization was performed on
followed cationic polymerization theory [27]. But the reaction car-
a XPA-1 photochemical reactor, with 300 W Hg light source, and the
ried out so rapidly that disadvantage to both experiment research
rolling rate was 20 rpm, the wavelength of the radiation light was
and plant application. This limited the use of a wide range of vinyl
selected as 365 nm. Molecular weight and molecular weight distri-
monomers in polymerization. As such it needs an excellent method
bution of the polymers were measured by PL GPC 50 at 25 ◦ C using
to address the problem of HPMs mediated cationic polymerization.
THF as eluent against polystyrene standards, flow rate: 1 mL/min,
One of the best methods was selecting a suitable ligand to stable
sample concentration: 1 mg/mL.
the active center during polymerization.
In present paper, 4,4 -Bipyridine was used for modifying the
stability of 12-tungstophosphoric acid. The compound was struc- 2.2. Catalyst preparation
turally characterized by elemental analysis, IR spectroscopy and 1 H
NMR spectroscopy. The electrochemical property was determined H3 PW12 O40 ·16.5H2 O of 6.35 g (0.002 mol) was dissolved in
24 ml of ethanol and heated at 40 ◦ C for 30 min under stirring. Then
0.93 g of [(C5 H4 )N]2 (0.006 mol) in ethanol (58 ml) was added to the
solution dropwise under stirring. The solution was stirred contin-
∗ Corresponding author. Fax: +86 512 52251842. uously for 8 h. The resultant precipitate was filtrated and washed
E-mail address: chendy@cslg.edu.cn (D. Chen). with ethanol. After drying in a vacuum oven at 30 ◦ C for 12 h, a

1381-1169/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molcata.2012.06.009
196 D. Chen et al. / Journal of Molecular Catalysis A: Chemical 363–364 (2012) 195–199

white powder catalyst was obtained. Yield: 36.2 mg (based on W).

Anal. Calcd for C15 H15 N3 O40 PW12 : C:5.77; N:1.35; H:0.48%. Found:
C:5.71; N:1.29; H:0.51%.

2.3. Electrochemical property determination

All electrochemical measurements were carried out with CHI

660 electrochemistry workstation. A three-electrode set up was
employed for the electrochemical studies, Gold (Au) was utilized
as working electrode, modified with the complex acetone solu-
tion. A platinum disk was used as the counter electrode, and the
reference electrode was a saturated calomel reference electrode
(SCE). Before used, the oxidized gold working electrode surfaces
were generated by applying 2.0 V vs. SCE for 90 s in 2 M NaOH
solution.

2.4. Typical polymerization process

The catalysis activity test of 4,4 -Bipyridine phosphotungtic salt

is performed as follows: [(C5 H4 )N]3 (PW12 O40 ) of 0.29 g (0.1 mmol)
was mixed with 10 g of acetone in a quartz reaction tube, stirred
by magnetic power. Dry nitrogen was input for about 20 min to
eliminate the effect of possible air, and then 0.10 g (10 mmol) of
vinyl monomer was added. The polymerization was performed
on a XPA-1 photochemical reactor, with 300 W Hg light source
and the rolling rate was 20 rpm, the wavelength of the radiation
light was selected as 365 nm. The polymerization was terminated
by addition of acidic methanol, The polymer product was pre-
cipitated into 50 ml methanol, filtered, washed with methanol,
and dried in a vacuum oven at 50 ◦ C overnight to a constant
weight.
Gel permeation chromatography (GPC) analyses of polymer
samples were carried out at 25 ◦ C using THF as eluent on a Polymer
Laboratory-50 instrument and calibrated using monodispersed
polystyrene standards at a flow rate of 1.0 ml/min. Number-average
molecular weight and polydispersity of polymers were given rela-
tive to PS standards.
3. Results and discussion
3.1. IR analysis
Fig. 1 shows the FT-IR spectra of the as-prepared catalysts:
H3 PW12 O40 (a), [(C5 H4 )N]3 (PW12 O40 ) (b), and the catalyst after
polymerization (c). Over a range of 800–1100 cm−1 , the absorp-
tion bands around 1080, 985, 896, and 804 cm−1 , corresponding to
the four characteristic skeletal vibrations of the Keggin oxoanions,
were observed in the FT-IR spectra of samples (a). These absorption
bands are attributed to the vibrations of as(P Oa ), as(W Od ),
as(W Ob W) in corner shared octahedra, and as(W Oc W) in
edge shared octahedra, respectively [29–31]. For the FT-IR spec-
trum of sample (b) and (c), the absorption band at 1080 cm−1 is
attributed to the vibration of as(P Oa ), the absorption bands of
as(W Od ), as(W Ob W) and as(W Oc W) shift to 980 (for
b and c), 893 (for b, 895 for c), 798 (for b, 799 for c) cm−1 . These
shifts indicate the changes of the bond length and bond angle. Com-
pared with the spectra of sample (a), the intensities of these bands
of sample (b) and (c) did not change, which indicated two means:
one is that the Keggin structure was not destroyed after modi-
fied by quaternary ammoniums; secondly, no change was found
during the catalytic polymerization. The possible reason of these
band changes is that the MoO6 octahedra of the polyanions were
distorted in some degrees because of the influence of the outer
quaternary ammonium cations.
Fig. 1. IR analysis (a) phosphotungtic acid; (b) 4,4 -bipyridine phosphotungtic salt;
(c) the catalyst after polymerization.
1H
3.2. NMR analysis
1H NMR analysis was an important method for studying
the reactions catalyzed by phosphotungtic compound [27,32]. In
Fig. 2a, the peak at 5.416 ppm was attributed to the protons in
phosphotungtic acid, and the peak at 2.475 ppm was attributed to
the solvent of CD3 COCD3 . That was, all of the protons in phospho-
tungtic acid were in the same chemical environments. Fig. 2b was
the 1 H NMR spectrum of 4,4 -bipyridine, 7.88 ppm and 8.71 ppm
were attributed to H1 and H2 (see the formula in Fig. 2), and
3.38 ppm was attributed to the possible structural water. After reac-
tion (Fig. 2c), the peak at 5.416 disappeared and a new peak at
5.993 ppm appeared, which might indicated the protons had trans-
ferred from phosphotungtic acid to the N atom of 4,4 -bipyridine
unit. The peaks of H1 and H2 were shifted to 8.36 ppm and 9.01 ppm
respectively. The possible reaction was deduced as follows:
3.3. Electro-chemical property analysis
Fig. 3 showed cyclic voltammograms (CVs) of the aimed prod-
uct in 0.5 M buffer solution of HAc-NaAc with different scan rate.
Three groups of redox peak could be observed, peak II and III
were very small (illustrate B), while peak I was strong. Redox
potential was shown at 1.08 and 0.57 when the scan rate was
selected as 100 mV/s. With increasing of the scan rate, the oxidation
peak potential shifted to more positive and the reduction potential
shifted to more negative, while the peak currents increased lin-
early with increasing of the square of scan rate (illustrate A). This
revealed that the electrochemical behavior of the complex chem-
sorbed on the surface of the ligands showing diffusion confined
redox process [33].
Additionally, the electrode modified by the complex had highly
stability. In 0.5 M buffer solution of HAc-NaAc and potential range
 D. Chen et al. / Journal of Molecular Catalysis A: Chemical 363–364 (2012) 195–199 197

Fig. 2. 1
H NMR spectra (a) phosphotungtic acid; (b) 4,4 -bipyridine; (c) 4,4 -bipyridine phosphotungtic salt.

of −0.4–1.6 V, the peak currents had not any weakening after scan- 3.4. Catalytic activity
ning for 300 times even laying aside for 2 months. This indicated
the potential application in both chemical sensor and recovery The catalytic polymerization of vinyl monomer, styrene is pre-
catalyst. sented as a sample. Polymerizations of styrene with this catalyst
proceed readily under a 359 nm light radiation for 60 min at
room temperature. This is a fast and smooth reaction when com-
pared to the polymerization initiated by phosphotungtic acid [27].
The increase in rate is manifested by a lowering of molecular
I weight from 9300 to 5330, and broadening of the polydisper-
7
sity from 1.29 to 2.01, which is ascribed to the chain transfer
A 6 reaction [34]. These observations led us to lower the reaction
40 400 5 temperature and radiation power, in attempt to avoid excessive
4 chain transfer reaction. Polymerization proceeds efficiently at reac-
i/

200
3 tion 3 reaching 92% conversion after 60 min at 20 ◦ C and 300 W
20 power. When the molar ratio of monomer to initiator was doubled
2
0 from 50 to 100, an approximate doubling of the Mn is observed
6 12 18 24 1
1/2 (entries 3 and 9, Table 1), as would be expected for a controlling
V
I/ A

0
polymerization.
III Styrene, vinyl iso-butyl ether, methyl methacrylate, and butyl
3 II B acrylate were used, as representative of the vinyl monomers, for
2 the photo-polymerization initiated by 4,4 -bipyridine phospho-
-20
tungtic salt (entries 3, 10, 11 and 12, Table 1). All reactions at
I/ A

1
20 ◦ C and 300 W showed very good first-order kinetic behavior
I' 0
'
(Fig. 4) indicating a low amount of chain transfer reaction under
-40 -1
II III these conditions. This taken together with the relatively narrow
'

0.0 -0.3
PDI values and high Mn of the products indicates that the polymer-
E/v ization shows controlled characteristics. Fig. 5 shows the evolution
of the Mn as a function of [M]/[I] for reaction 3, 10, 11 and 12,
1.6 1.2 0.8 0.4 0.0 -0.4
which increases linearly again as would be expected for controlling
E/v polymerization.
4,4 -bipyridine phosphotungtic salt is only soluble in high polar
Fig. 3. Cyclic voltammograms of gold/complex electrode (solid line) in a 0.5 M buffer
solvent such as dimethyl sulfoxide, which in turn is immiscible with
solution of HAc-NaAc. 1–7: 20, 50, 100, 200, 300, 400, and 500 mV s−1 (from inside
to outside); (A) the variation of cathodic peak current with scan rate; (B) peak II and other organic solvents such as toluene. This allows the reaction
peak III. solution to be washed with toluene so as to extract the catalyst,
198 D. Chen et al. / Journal of Molecular Catalysis A: Chemical 363–364 (2012) 195–199

Table 1
Final molecular weight and conversion data for the polymers synthesized in this work.

Reactiona Temperature/◦ C Time/min Power/W Conversion/%b Mnc PDIc

d
1 20 40 300 82 6507 1.40
2d 20 50 300 90 8921 1.32
3d 20 60 300 92 9300 1.29
4d 30 60 300 92 9036 1.33
5d 40 60 300 93 7989 1.60
6d 50 60 300 96 5833 1.98
7d 20 60 500 95 7754 1.88
8d 20 60 800 98 5330 2.01
9d * 20 120 300 78 17,305 1.32
10e 20 60 300 95 44,771 1.43
11f 20 60 300 89 6329 1.35
1g 20 60 300 88 7056 1.32
a
All reactions carried were 50% v/v in acetone.
b
Coversion from integration of 1 HNMR.
c
Determined using PL GPC-50 against polystyrene standards.
d
Vinyl monomer: styrene; [monomer]:[initiator]: 50:1.
d*
[monomer]:[initiator]: 100:1.
e
Vinyl monomer: vinyl iso-butyl ether.
f
Vinyl monomer: methyl methacrylate.
g
Vinyl monomer: butyl carylate.

Fig. 6. The recovery results of the catalyst.

Fig. 4. First order rate plots for the polymerization. () Polymerization of styrene,
(䊉) polymerization of vinyl iso-butyl ether, () polymerization of methyl methacry-
late, () polymerization of butyl acrylate. changed random between 6208 and 8640, PDI was changed ran-
dom between 1.12 and 1.83), which indicated that 4,4 -bipyridine
which allowing isolation of the catalyst from the polymer solution phosphotungtic salt was a recovery catalyst, and could repeat 10
for potential reuse. After 10 cycle reuse in styrene polymeriza- times at least.
tion (see Fig. 6), catalyst recovery is up to 96.7%, molecular weight
and polydispersity of polystyrene retained a stable level (Mn was
4. Conclusion

In summary, 4,4 -bipyridine phosphotungtic salt is an excellent

catalyst for the polymerization of vinyl monomers. Polymerizations
show controlled characteristics, and the catalyst can be isolated
from polymer product easily and reused for at least 10 times.

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Fig. 5. Evolution of molar mass with [M]/[I] for polymerization, line draw is the
linear regression fit through the data. () Polymerization of styrene, () polymer-
ization of vinyl iso-butyl ether, () polymerization of methyl methacrylate, ()
polymerization of butyl acrylate.
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