Synthesis of diphenyl carbonate from dimethyl carbonate and

phenol using O
2
-promoted PbO/MgO catalysts
Min Cao
a
, Yuezhong Meng
a,
*
, Yixin Lu
b
a
State Key Laboratory of Optoelectronic Materials and Technologies, Sun Yat-Sen University, Guangzhou 510275, PR China
b
Department of Chemistry and Medicinal Chemistry Program of the Oce of Life Sciences, National University of Singapore,
3 Science Drive 3, Singapore 117543, Singapore
Received 12 May 2005; accepted 7 July 2005
Available online 17 October 2005
Abstract
Various heterogeneously supported PbO catalysts were prepared for the synthesis of diphenyl carbonate (DPC) by transesterication
of dimethyl carbonate (DMC) with phenol. MgO was found to be the best support, and the modication by oxygen further enhanced the
catalytic activities of PbO/MgO catalysts. Several parameters aecting the transesterication were investigated. The yields of methylphe-
nyl carbonate (MPC) and DPC reached 10% and 26.6%, respectively, over 10 wt% O
2
-promoted PbO/MgO catalyst which was prepared
by impregnation method. X-ray diraction (XRD), dierential thermal analysis (DTA) and BrunauerEmmetTeller (BET) technique
were employed for the characterization of prepared catalysts. It was discovered that the structure and the oxidation states of lead species
in PbO/MgO catalysts changed after the promotion by oxygen.
2005 Elsevier B.V. All rights reserved.
Keywords: Diphenyl carbonate; Dimethyl carbonate; Transesterication; O
2
-promoted PbO/MgO
1. Introduction
Diphenyl carbonate (DPC) is an important chemical
intermediate, which has been used extensively for the pro-
duction of many organic and polymer materials, it is partic-
ularly valuable for the synthesis of polycarbonate since the
use of highly toxic phosgene can be avoided [13]. There are
a number of methods available for the preparation of DPC,
and the major ones include phosgenation method, oxidative
carbonylation of phenol and transesterication of phenol
and dimethyl carbonate (DMC). The obvious disadvan-
tages of phosgenation technique are the use of corrosive
and highly toxic phosgene as a raw material and the forma-
tion of hydrogen chloride as a by-product. Oxidative car-
bonylation of phenol is a prospective route for the
synthesis of DPC, but the use of noble catalyst and the
low yield of DPC limit its application. Transesterication
of phenol with DMC is the most suitable method for
an industrial production of DPC, which can be promoted
by eective catalysts. This route is a two-step process,
including the transesterication of DMC and phenol to
methylphenyl carbonate (MPC) (Eq. (1)) and the transeste-
rication of MPC and phenol to DPC (Eq. (2)) or the dis-
proportion of MPC to DPC and DMC (Eq. (3)).
OH CH
3
OH
O C O CH
3
O
H
3
C O C O CH
3
O
+ + 1
O C O CH
3
O
OH CH
3
OH + +
O C O
O
2
H
3
C O C O CH
3
O
O C O
O
O C O CH
3
O
+ 2 3
Transesterication of DMC and phenol is usually car-
ried out in the liquid phase using homogeneous catalysts
such as Lewis acids and soluble organic tin, titanium and
aluminium compounds [46]. However, the use of homoge-
neous catalysts generally results in dicult separation of
1566-7367/$ - see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2005.07.020
*
Corresponding author. Tel.: +86 20 84114113.
E-mail addresses: stdpmeng@zsu.edu.cn (Yuezhong Meng), chmlyx@
nus.edu.sg (Yixin Lu).
www.elsevier.com/locate/catcom
Catalysis Communications 6 (2005) 802807
the nal product. Heterogeneous catalysts, on the other
hand, are much more attractive since the purication pro-
cess can be greatly simplied.
Fu and Ono [7] reported that MoO
3
/SiO
2
as the best cat-
alyst among various supported catalysts tested for both the
transesterication (Eq. (1)) and the disproportion (Eq. (3))
steps, and the yields of these two reactions were 17.1% and
38%, respectively. Kim and Lee [810] proposed a two-step
synthetic sequence over the supported TiO
2
/SiO
2
catalyst to
prepare DPC, which involved the initial gas-phase transe-
sterication of DMC with phenol leading to MPC and the
subsequent liquid-phase disproportion of MPC to generate
DPC. The yield of MPC for the rst step was 31.7%, but a
very high reaction temperature of 450 C was required. The
selective formation of DPC was feasible in the second step
and the yield of DPC approached 47%. Zhou et al. [11] pre-
pared a novel heterogeneous leadzinc double oxide cata-
lyst. Their experimental results showed that Pb
3
O
4
was
the main active species, and amorphous ZnO played a role
as the promoter. Under the conditions of calcination tem-
perature of 500 C and a ratio of Pb/Zn at 2:1, the highest
DPC yield of 45.6% was attainable. However, the yield of
DPC dropped to 24.3% when the catalyst was re-used for
the second time. It was recently reported that samarium tri-
uoromethanesulfonate (Sm(OTf)
3
) served as a novel solid
catalyst for the synthesis of DPC by transesterication of
DMC with phenol [12]. The samarium catalyst worked well
both in aqueous media and in the air, and it was reusable.
Lead oxides [13] are known to eectively catalyze the
transesterication of DMC with phenol, but such catalysts
are dicult to recover from product. Herein, we report a
novel, highly ecient catalytic system in which lead oxides
are supported on MgO for the production of DPC via the
transesterication between DMC and phenol.
2. Experimental
2.1. Chemical reagents
DMC (Shandong Shida Shenghua Chemical Co., China)
was fractionally distilled and stored over molecular sieve
(4 A

). Phenol was of analytical reagent (AR) grade and

used without further purication. AR grade lead nitrate
and ammonia were used for the preparation of catalysts.
Various supports (MgO, TiO
2
, nano-SiO
2
, colloidal-SiO
2
,
c-Al
2
O
3
and HZSM38 molecular sieve) were commercially
available and used as received.
2.2. Preparation of catalysts
Non-promoted PbO/MgO was prepared by three meth-
ods: impregnation, co-precipitation and mechanical mill-
ing. In impregnation, MgO was impregnated with an
aqueous solution of lead nitrate. The mixture was dried
at 110 C for 12 h and then calcinated at 500 C for 3 h.
In co-precipitation, an aqueous solution of ammonia was
added into an aqueous mixture of MgO and lead nitrate.
The resulting solution was stirred for 30 min and aged
for 12 h. The sediment was ltered under vacuum, then
dried and calcinated as described in the impregnation pro-
cess. In the mechanical milling method, lead nitrate and
MgO were mixed in a certain ratio and milled uniformly,
then calcinated at 500 C for 3 h. Oxygen-promoted PbO/
MgO was prepared by oxidizing PbO/MgO in a ow of
oxygen at 460 C for 4 h. Other supported PbO catalysts
such as PbO/TiO
2
, PbO/nano-SiO
2
, PbO/colloidal-SiO
2
,
PbO/c-Al
2
O
3
and PbO/HZSM38 were prepared by impreg-
nation method as described above.
2.3. Characterization
Wide-angle X-ray diraction (WAXD) measurement
was performed at room temperature using a Rigaku
D/max-1200X diractometer with 2h scan range of 580,
a scanning rate and gradient at 5/min and 0.05,
respectively.
The thermal behaviors of the catalysts were studied
using a PerkinElmer Thermogravimetric/Dierential
Thermal Analyzer under the protection of nitrogen atmo-
sphere. The temperature was scanned from 30 to 1100 C
with increments of 10 C/min. The specic surface areas
of the catalysts were determined by the Brunauer
EmmetTeller (BET) technique using a Quantachrome
BET analyzer (model: NOVA 1000).
2.4. Reaction procedure
The reaction was carried out in a 250 ml four-neck
round-bottom ask equipped with a dropping funnel, a
nitrogen inlet and a fractional column connected to a liquid
dividing head. Phenol (270 mmol) and the catalyst were
added under nitrogen, the resulting mixture was then heated
to 180 C. Subsequently, DMC (330 mmol) was added
drop-wise. As the reaction proceeded, an azeotropic mix-
ture of methanol and DMC (70/30) with a boiling temper-
ature of 6263 C was fractionally distilled out. After the
addition of DMC, the reaction mixture consisted of a large
quantity of MPC and a small amount of DPC. Continuous
distillation of DMC and methanol shifted the equilibrium
of Eqs. (2) and (3) to the direction of forming DPC, facili-
tating the conversion of MPC to DPC. After 810 h, the
catalyst was removed by ltration. The reaction mixture
was then examined on a gas chromatograph equipped with
a ame ionization detector, and the structures of resulted
compounds were characterized by mass spectrometry.
3. Results and discussion
3.1. Catalytic behavior
Table 1 shows the catalytic activities of various sup-
ported lead oxide catalysts in the transesterication of
DMC and phenol. The loading of lead oxide was 10 wt%
of the supported catalyst. In certain entries, a trace amount
M. Cao et al. / Catalysis Communications 6 (2005) 802807 803
of anisole was detected as by-product due to the methyla-
tion of phenol by DMC. The eects of supports on the cat-
alytic activities of PbO were carefully studied. The most
ecient support was MgO. Whereas the yield of DPC
was 14.4% over 0.15 g of PbO alone (entry 1), DPC yield
was greatly improved when MgO-supported PbO of same
quantity was employed. The yields of MPC and DPC were
4% and 24.9%, respectively (entry 8) over 10 wt% non-
promoted PbO/MgO. As shown in entries 37, when other
supports were used, the catalytic activities of the resulting
supported PbO catalysts were lower than that of PbO
alone. When the PbO/MgO catalyst was promoted with
oxygen, the yields of MPC and DPC were improved to
10% and 26.6%, respectively. The catalytic activity of the
O
2
-promoted PbO/MgO catalyst prepared by impregna-
tion (entry 9) was slightly higher than that of the O
2
-pro-
moted catalysts prepared by co-precipitation (entry 10)
and mechanical milling (entry 11).
It should be noted that the supported catalysts are recy-
clable and reusable. In the end of the reaction, the O
2
-
promoted PbO/MgO catalyst was easily separated from
reaction mixture by ltration. Such catalysts can be regen-
erated by drying at 110 C and subsequent calcination at
460 C in a ow of oxygen. When the same reactions were
carried out using regenerated O
2
-promoted PbO/MgO cat-
alyst, DPC was obtained in a yield comparable to that of
reaction utilizing fresh catalyst. However, the yield of
MPC was lower for the regenerated catalyst, presumably
due to the change of the crystal state of lead oxide during
the regeneration process.
Fig. 1 correlates DPC yields with the amounts of PbO on
MgO support. The reaction temperature was kept at 180 C
and the total weight of the O
2
-promoted PbO/MgO catalyst
was 1 g. DPC yield increased with the increase of PbO load-
ing in the supported catalyst and reached constant value
when the amount of PbO reached 10 wt%.
Fig. 2 shows the relationship between DPC yields and
the amounts of O
2
-promoted PbO/MgO catalyst at
180 C. The loading of PbO on MgO support was kept at
10 wt%. The highest yield of DPC at 26.6% was reached
when 1.5 g catalyst was used, and remained constant even
when more catalysts were employed.
3.2. X-ray diraction
The structure and the chemical state of lead oxide spe-
cies on MgO were investigated by X-ray diraction.
Fig. 3 shows the results of XRD analyses for the non-
promoted PbO/MgO catalysts with dierent PbO loadings.
Table 1
The catalyst activities of supported lead oxides for the synthesis of diphenyl carbonate
No. Catalyst Phenol conversion (%) Yields (%)
MPC DPC Anisole
1 PbO (0.15 g) 22.0 7.6 14.4 0.0
2 MgO (1.5 g) 7.2 5.3 1.9 0.0
3 PbO/HZSM38 0.6 0.6 0.0 0.0
4 PbO/nano-SiO
2
5.1 2.4 2.7 0.0
5 PbO/TiO
2
5.2 2.4 2.8 0.0
6 PbO/c-Al
2
O
3
13.0 6.0 7.0 0.0
7 PbO/colloidal-SiO
2
13.7 4.8 8.9 0.0
8 Non-promoted PbO/MgO 29.0 4.0 24.9 0.1
9 O
2
-promoted PbO/MgO 36.8 10.0 26.6 0.2
10 O
2
-promoted PbO/MgO
a
26.1 6.0 20.0 0.1
11 O
2
-promoted PbO/MgO
b
27.3 4.4 22.7 0.2
12 O
2
-promoted PbO/MgO
c
32.9 5.7 27.1 0.1
Reaction conditions: catalyst, 1.5 g; loading of lead oxide on supports, 10 wt%; loading method, impregnation; Phenol, 270 mmol; DMC, 330 mmol;
temperature, 180 C.
a
Loading method: co-precipitation.
b
Loading method: mechanical milling.
c
Recycle use of the regenerated catalyst.
0 10 20
0
10
20
30
D
P
C

y
i
e
l
d

/

%

Loading of PbO / wt%
Fig. 1. Eect of the PbO loading on MgO on the DPC yield in the
transesterication of DMC and phenol: catalyst, O
2
-promoted PbO/MgO;
loading method, impregnation; amount of catalyst, 1 g; phenol, 270 mmol;
DMC, 330 mmol; temperature, 180 C.
804 M. Cao et al. / Catalysis Communications 6 (2005) 802807
At low PbO loadings, the PbO phase was not observed.
Characteristic peaks of a-PbO were detected for non-pro-
moted PbO/MgO catalysts when the PbO loadings were
greater than 10 wt%. X-ray diraction patterns of the O
2
-
promoted PbO/MgO catalysts with dierent PbO loadings
are depicted in Fig. 4. From the comparison of peak inten-
sities in the XRD patterns of the non-promoted and O
2
-
promoted PbO/MgO catalysts, it was quite obvious that
a-PbO peaks decreased dramatically in the latter case.
Apart from the peaks of a-PbO, weak peaks corresponding
to two other lead oxide species, Pb
3
O
4
and PbO
1.37
, were
also observed for the O
2
-promoted PbO/MgO catalyst with
a loading of 20 wt% PbO. These results suggest that lead
oxides in the O
2
-promoted PbO/MgO catalysts may exist
in microcrystalline structure or amorphous state, and the
oxidation state of lead is partially dierent from the non-
promoted PbO/MgO catalysts. As a result of the change
of oxidation state and crystal state of lead, the catalytic
activity of O
2
-promoted PbO/MgO catalysts was slightly
higher than that of non-promoted PbO/MgO catalysts.
3.3. Dierential thermal analysis
The thermal behaviors of dierent PbO/MgO catalysts
are showed in Fig. 5. The appearance of endothermic ef-
fects at about 881 C on both PbO and Pb
3
O
4
samples were
due to the sublimation of lead oxides. Furthermore, Pb
3
O
4
exhibited another endothermic peak at 564 C, which was
attributed to the transformation of Pb
3
O
4
to PbO. MgO
support did not show any endothermic peaks. Obvious
endothermic eects were not observed on the DTA curve
of 10 wt% O
2
-promoted PbO/MgO, which was the result
of strong interaction between PbO and MgO support. As
shown in the DTA curve of 20 wt% O
2
-promoted PbO/
MgO (curve E), there were two endothermic peaks at 507
and 887 C, corresponding to the transformations of
Pb
3
O
4
to PbO and the sublimation of PbO, respectively.
This result indicated that Pb
3
O
4
existed in the lead rich
sample, which was consistent with the XRD analyses of
the O
2
-promoted PbO/MgO (Fig. 4). In the absence of
Pb
3
O
4
, 20 wt% non-promoted PbO/MgO did not show
the endothermic eect at 564 C.
DTA curve of O
2
-promoted PbO/MgO prepared by
dierent methods are presented in Fig. 6. No obvious endo-
thermic eects were observed for the sample of O
2
-
promoted 10 wt% PbO/MgO prepared by the methods of
0 1 2 3
10
20
30
D
P
C

y
i
e
l
d

/

%
Amount of Catalyst / g
Fig. 2. Eect of the amount of catalyst on the DPC yield in the
transesterication of DMC and phenol: catalyst, O
2
-promoted PbO/MgO
(10 wt%); loading method, impregnation; phenol, 270 mmol; DMC,
330 mmol; temperature, 180 C.
0 10 20 30 40 50 60 70 80 90
5%
2 / degree
10%
15%
20%
PbO wt%
Fig. 3. X-ray diraction patterns of non-promoted PbO/MgO catalysts
with dierent PbO loading. Loading method, impregnation: (r) a-PbO.
0 10 20 30 40 50 60 70 80 90
PbO wt%
5%
2 / degree
10%
15%
20%
Fig. 4. X-ray diraction patterns of O
2
-promoted PbO/MgO catalysts
with dierent PbO loading. Loading method, impregnation: (r) a-PbO;
(h) Pb
3
O
4
; (}) PbO
1.37
.
M. Cao et al. / Catalysis Communications 6 (2005) 802807 805
impreg- nation or co-precipitation. Nevertheless, two peaks
at 538 and 903 C appeared for the 10 wt% O
2
-promoted
PbO/MgO catalyst prepared by mechanical milling, which
indicated a weak interaction between the catalyst and the
support when the catalyst was prepared by such a method.
DTA curves of regenerated O
2
-promoted PbO/MgO are
shown in Fig. 7. After the reaction, catalyst was separated
by ltration and then dried at 110 C. The catalyst was
regenerated by calcination at 460 C in a ow of oxygen.
There was an obvious exothermic eect at 965 C on the
DTA curve of catalyst, which may due to the crystal trans-
formation of PbO. After calcination at 460 C in a ow of
oxygen, the DTA curve of regenerated catalyst was very
similar to that of fresh catalyst.
3.4. Specic surface area
The BET surface areas of MgO support, 10 wt% non-
promoted PbO/MgO catalyst and 10 wt% O
2
-promoted
PbO/MgO catalyst were 33.96, 21.64 and 19.25 m
2
/g,
respectively. After modication by oxygen, the BET sur-
face area of PbO/MgO catalyst decreased slightly. The
BET surface areas of 10 wt% O
2
-promoted PbO/MgO cat-
alysts prepared by methods of impregnation, co-precipita-
tion and mechanical milling were 19.25, 32.42 and
25.47 m
2
/g, respectively. Therefore, the O
2
-promoted
PbO/MgO catalyst prepared through impregnation meth-
od possessed the smallest BET surface area, and the highest
catalytic activity. The regenerated O
2
-promoted 10 wt%
PbO/MgO prepared by impregnation has a BET surface
area of 19.98 m
2
/g, which is similar to the fresh O
2
-
promoted PbO/MgO prepared using the same method.
4. Conclusion
Among various supported PbO catalysts, PbO/MgO
showed the highest activity and selectivity for the transeste-
rication of dimethyl carbonate with phenol. Modication
0 200 400 600 800 1000 1200
T /
o
C
C
883
o
C
507
o
C
881
o
C
564
o
C
887
o
C
B
D
E
F
A
Fig. 5. DTA analysis of PbO/MgO catalysts. Loading method, impreg-
nation: (A) PbO; (B) Pb
3
O
4
; (C) MgO; (D) O
2
-promoted PbO/MgO
(10 wt%); (E) O
2
-promoted PbO/MgO (20 wt%); (F) un-promoted PbO/
MgO (20 wt%).
0 200 400 600 800 1000 1200
T /
o
C
C
D
903
o
C
B
538
o
C
E
A
881
o
C
564
o
C
Fig. 6. DTA analysis of O
2
-promoted PbO/MgO catalysts prepared
by dierent methods. PbO loading, 10 wt%: (A) PbO; (B) Pb
3
O
4
;
(C) O
2
-promoted PbO/MgO (impregnation); (D) O
2
-promoted PbO/MgO
(co-precipitation); (E) O
2
-promoted PbO/MgO(mechanical milling).
0 200 400 600 800 1000 1200
T /
o
C
C
B
965
o
C A
Fig. 7. DTA analysis of regenerated O
2
-promoted PbO/MgO catalysts.
PbO loading, 10 wt%; loading method, impregnation: (A) fresh catalyst;
(B) catalyst used; (C) catalyst used and calcinated at 460 C in owing
oxygen.
806 M. Cao et al. / Catalysis Communications 6 (2005) 802807
by oxygen can improve the catalytic activities of PbO/MgO
catalysts. Preparation by impregnation method rendered
slightly higher activity to the O
2
-promoted PbO/MgO cat-
alyst than co-precipitation or mechanical milling method.
When 10 wt% O
2
-promoted PbO/MgO catalyst by impreg-
nation method was used, the yields of methylphenyl car-
bonate and diphenyl carbonate based on phenol were
10% and 26.6%, respectively. The O
2
-promoted PbO/
MgO catalysts could be regenerated and reused with al-
most the same eciency as that of fresh catalyst. The rea-
son of the activity enhancement of PbO/MgO catalysts by
oxygen modication could be ascribed to the changes of
oxidation state and crystal structure of lead, which was
supported by XRD and DTA data. DTA analyses sug-
gested that there existed strong interaction between PbO
and MgO support in the O
2
-promoted PbO/MgO catalysts.
Acknowledgments
We thank the Ministry of Science and Technology of
China (Grant No. 2002BA653C), Natural Science Founda-
tion of Guangdong Province (Excellent Team Project,
Grant No. 015007), Key Strategic Project of Chinese
Academy of Sciences (Grant No. KJCX2-206B) and Key
Project of Guangzhou Science and Technology Bureau
for nancial support of this work. Y. Lu wishes to thank
National University of Singapore for nancial support.
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