An active and heterogeneous catalyst for synthesis of diphenyl carbonate

Article abstract of DOI:10.14233/ajchem.2015.17079

Zn₄O[(O₂C)-C₆H₄-(CO₂)]₃ was prepared by solvothermal method and characterized with XRD and FT-IR. Zn₄O[(O₂C)-C₆H₄-(CO₂)]₃ was used as the catalyst for the synthesis of diphenyl carbonate via the transesterification dimethyl carbonate and phenol and its catalytic activity was compared with Ti(OBu)₄, Mg-Al Mg-Al LDH and Zn-Al Mg-Al LDH. The results show that Zn₄O[(O₂C)-C₆H₄-(CO₂)]₃ is an active and heterogeneous catalyst for the synthesis of diphenyl carbonate via the transesterification.

Full text of DOI:10.14233/ajchem.2015.17079

Asian Journal of Chemistry; Vol. 27, No. 2 (2015), 613-615
ASIAN JOURNAL OF CHEMISTRY
http://dx.doi.org/10.14233/ajchem.2015.17079
An Active and Heterogeneous Catalyst for Synthesis of Diphenyl Carbonate
1,*
2
1
LIPING WANG , GONGYING WANG and FAN WANG
1
2
College of Chemistry and Chemical Engineering, Qujing Normal University, Qujing 655011, P.R. China
Chengdu Institute of Organic Chemistry, Chinese Academy of Science, Chengdu 610041, P.R. China
*
Corresponding author: Tel: +86 874 8998658; E-mail: wanglp_csu@163.com
Received: 20 January 2014;
Accepted: 22 April 2014;
Published online: 10 January 2015;
AJC-16630
Zn
used as the catalyst for the synthesis of diphenyl carbonate via the transesterification dimethyl carbonate and phenol and its catalytic
activity was compared with Ti(OBu) , Mg-Al Mg-Al LDH and Zn-Al Mg-Al LDH. The results show that Zn O[(O C)-C -(CO )] is an
4
O[(O
2
C)-C
6
4
H -(CO
)]
2 3
was prepared by solvothermal method and characterized with XRD and FT-IR. Zn
4
O[(O
2
C)-C H
6 4
-(CO
2
3
)] was
4
4
2
6
H
4
2
3
active and heterogeneous catalyst for the synthesis of diphenyl carbonate via the transesterification.
Keywords: Diphenyl carbonate, Transesterification, Dimethyl carbonate, Catalyst.
INTRODUCTION
EXPERIMENTAL
Diphenyl carbonate (DPC) is a potential substitute material
The zinc nitrate hexahydrate (Zn(NO
Shanghai Xinbao Fine Chemical Plant), benzene-1,4-
dicarboxylic acid (H BDC, 99%, Shanghai Runjie Chemical
Reagent Co., Ltd.) and N,N-dimethylformamide (DMF, 99 %,
Shanghai Runjie Chemical Reagent Co., Ltd.) were used to
prepared MOFs.
The dimethyl carbonate (DMC, AR, Chongqing
Changfeng Chemical Plant) and phenol (AR, Shanghai Runjie
Chemical Reagent Co., Ltd. ) were used to prepare diphenyl
carbonate. All the reagents were used without any further
purification.
3
)·6H
2
O, 99 %,
1,2
for toxic phosgene in the synthesis of polycarbonate diol .
The transesterification between dimethyl carbonate (DMC)
and phenol is regarded as a more promising route for the
synthesis of diphenyl carbonate because dimethyl carbonate
is a green chemical and has been commercially produced the
oxidative carbonylation of methanol.
2
Several catalysts, such as Ti(OBu)
/SiO , Mg-Al-CO LDH and Zn-Al-CO
been developed for the transesterification between dimethyl
carbonate and phenol to diphenyl carbonate. Ti(OBu) and
Cp TiCl are homogeneous catalysts and show high catalytic
activities, but they are unstable and sensitive to the moisture
in the air. MoO /SiO , TiO /SiO , Mg-Al-CO LDH and Zn-
Al-CO LDH are heterogeneous catalysts and easy to be removed
4
, Cp
2
TiCl
2
, MoO
LDH , have
3
-6
/SiO
2
,
3
TiO
2
2
3
3
4
2
2
Preparation of catalyst: 1.36 g H
2
BDC and 4.84 g
Zn(NO )·6H O were dissolved in 160 mL N,N-dimethyl-
3
2
3
2
2
2
3
formamide. Then the solution was sealed in a 250 mL round
flask and kept at 100 ºC for 24 h. The precipitate was collected
by filtration and washed by N,N-dimethylformamide. The solid
3
from the product, but their catalytic activities are lower than
those of homogeneous catalysts. So the development of more
efficient catalysts is desirable.
Zn
4
O[(O
2
C)-C
6
H
4
-(CO
2
)] was dried at 90 ºC in vacuum and
3
7,8
then stored in a vacuum desiccator . The colorless crystalline
materials were characterized with Rigaku D/max 2500 PC X-
ray diffraction (XRD) and Nicolet PROTÉGÉ 460 Fourier
transform infrared (FTIR) spectroscopy.
Zn
4
O[(O
2
C)-C
6
H
4
-(CO
2
)]
O inorgnaic moiety to benzne-
C)-C -(CO )] has drawn more
3
can form a porous cubic
structure by connecting a Zn
,4-dicarboxylate . Zn
4
7
1
4
O[(O
2
H
6 4
2
3
and more attention due to its high surface area, microporosity,
well-defined structure and good chemical stability. In this work,
Preparation of diphenyl carbonate: 0.2 mol phenol and
Zn
4
O[(O
2
C)-C
6
H
4
-(CO
2
3
)] were placed in a 100 mL flask
Zn
4
O[(O
2
C)-C
6
H
4
-(CO
2
)]
3
was prepared by the solvothermal
equipped with a thermometer, a mechanical stirrer and a reflux
condenser. When the reactor temperature was increased to
160 °C at the nitrogen atmosphere, 0.4 mol dimethyl carbonate
method. Then it was used as a catalyst in the transesterification
between dimethyl carbonate and phenol.

614 Wang et al.
Asian J. Chem.
was added gradually to the reactor. This process continued
until there was no methanol distilled off.
Measurements: The X-ray diffraction (XRD) was under-
taken on a Rigaku D/max 2500 PC powder X-ray diffracto-
CO
were investigated in reactor.As shown in Table-1, Zn
-(CO )] exhibits highest catalytic activity.
The high catalytic activity of Zn O[(O C)-C
can be related to its framework structure. First, here are Lewis
acid sites and basic sites on the framework of Zn O[(O C)-
. The carbonyl carbon atoms in dimethyl
carbonate molecules become highly electrophilic because the
carbonyl oxygen atoms may coordinate with Lewis acid sites.
So it is easy for nucleophilic regents to attack the carbonyl
carbon atoms in dimethyl carbonate molecules. And the
nucleophilicity of hydroxybutyl groups in phenol molecules
is improved because of the coordination of hydroxyl hydrogen
3
LDH, Zn-Al-CO
3
LDH and Zn
4
O[(O
2
C)-C
6
H
4
-(CO
2
)]
3
4
O[(O C)-
2
C
6
H
4
2
3
4
2
6
H
4
-(CO
)]
2 3
meter using CuK radiation. Infrared spectroscopy (FTIR) was
α
recorded in a Nicolet 560 FTIR spectrometer. The specific
surface area measurement and pore analysis was carried out
on a Micromeritics ASAP 2020 V3.00 H (USA) surface area
4
2
9
,10
C
6
H
4
-(CO
2
)]
3
analyzer by N adsorption at 77 K. A Shimadzu GC-2010 gas
2
chromatograph equipped with a flame-ionization detector was
used to qualitatively and quantitatively analyze the distillate.
RESULTS AND DISCUSSION
atoms with basic sites on the framework of Zn
4
O[(O
2
C)-C
6
H
4
-
Characterization of catalyst: Fig. 1 shows the FTIR
(
CO )] . Second, Zn O[(O C)-C -(CO )] has higher surface
2
3
4
2
6
H
4
2
3
spectrum of Zn
4
O[(O
2
C)-C
6
H
4
-(CO
2
)] prepared by the solvo-
3
-1
area, porosity and well-defined structure. Thus the carbonyl
carbon atoms in dimethyl carbonate molecules and hydroxyl
hydrogen atoms in phenol molecules are easier to coordinate
with Lewis acid sites and basic sites on the framework of
thermal method. The peaks at 1593 and 1504 cm correspond
to the asymmetric stretching vibration of -COO. The peaks at
402 and 1321 cm are attributed to the symmetric stretching
-1
1
-1
vibration of -COO. The peaks at 1153, 1151 and 1016 cm
Zn
4
O[(O
2
C)-C
6
H
4
-(CO
2
3
)] , respectively. Third, the good
crepresent the in-plane bending vibration of C-H. The peaks
-
1
chemical and thermal stability of Zn O[(O C)-C H -(CO )]
4
2
6
4
2
3
at 827, 762 and 598 cm correspond to the out-of-plane
bending vibration of C-H. Fig. 2 shows the XRD pattern of
framework also contribute its higher catalytic activity.
Zn
reflection peaks are observed at 8.8 , 14.08, 15.62, 17.64,
8.58, 30.40, 31.02 and 36.68º, which are well matched with
4
O[(O
2
C)-C
6
H
4
-(CO
2
)]
3
. As shown in Fig. 1, the sharp
TABLE-1
EFFECT OF DIFFERENT CATALYSTS
ON THE TRANSESTERIFICATION
2
8
the reported peaks .
Selectivity (%) Selectivity (%)
Catalyst
Yield (%)
MPC DPC
MPC+DPC
95.7
80
60
40
20
0
Ti(OBu)4
62.7
48.9
51.6
71.2
41.3
33.6
36.6
41.7
18.7
10.1
12.1
27.2
Mg-Al-CO LDH
89.4
94.3
96.7
3
Zn-Al-CO LDH
3
Zn O[(O C)-C H -(CO )]
3
4
2
6
4
2
Reaction conditions: n(phenol): n(DMC) = 2, w(catalyst) = 1 %, time =
o
1
0 h, temperature = 160-180 C, DMC: dimethyl carbonate, MPC:
methyl phenyl carbonate, DPC: diphenyl carbonate
Effect of the amount of the catalyst on the synthesis of
diphenyl carbonate: Table-2 shows the effect of catalyst
Zn O[(O C)-C H -(CO )] on the synthesis of diphenyl
3600
2800
2000
1200
400
4
2
6
4
2
3
–
1
carbonate. It can be seen that, the amount of Zn O[(O C)-C H -
4
2
6
4
Wavenumber (cm )
(
CO
2
)]
3
has a notable effect on the transesterification.As shown
O[(O C)-C -(CO )]
Fig. 1. FTIR spectrum of Zn
4
O[(O
2
C)-C
6
H
4
2 3
-(CO )]
in Table-2, when the amount of Zn
4
2
6
H
4
2
3
30000
25000
20000
15000
10000
increases from 0.2 to 1 wt. %, the conversion of dimethyl
carbonate is increased to 71.2 % from 42.7 %. At the same
time, the yield of methyl phenyl carbonate is increased by
17.4 to 41.7 % and the yield of diphenyl carbonate is increased
by 11.3 to 27.2 %. However, above 1 %, the conversion of
dimethyl carbonate, yields of methyl phenyl carbonate and
diphenyl carbonate remain almost unchanged.
Effect of reaction time on the synthesis of diphenyl
carbonate: Table-3 shows the effect of reaction time on the
transesterification between dimethyl carbonate and phenol to
diphenyl carbonate. As shown in Table-3, when the reaction
time is increased from 2 to 10 h, the conversion of dimethyl
carbonate increases to 71.2 % from 16.2 %. At the same time,
the yield of methyl phenyl carbonate is increased by 30.1 %
to 41.7 and the yield of diphenyl carbonate is increased by
23.5 to 27.2 %. However, above 10 h, the conversion of dimethyl
carbonate, yields of methyl phenyl carbonate and diphenyl
carbonate remain almost unchanged.
5
000
0
0
20
40
60
80
2
θ
(°)
Fig. 2. XRD pattern of Zn
4
O[(O
2 6 4 2 3
C)-C H -(CO )]
Catalytic activity of Zn
Mg-Al-CO LDH and Zn-Al-CO
the transesterification between dimethyl carbonate and phenol
4
O[(O
2
C)-C
6 4
H
-(CO
2
)]
3
:Ti(OBu)
4
,
3
3
LDH are efficient catalysts for
3
-6
to diphenyl carbonate . For comparisons, Ti(OBu) , Mg-Al-
4

Vol. 27, No. 2 (2015)
An Active and Heterogeneous Catalyst for Synthesis of Diphenyl Carbonate 615
economical and the catalyst is heterogeneous and easier to
TABLE-2
EFFECT OF THE AMOUNT OF ZN O[(O C)-C H -(CO )]
3
4
2
6
4
2
separate from the product. Therefore, Zn
CO )] is an effective catalyst for synthesis of diphenyl
carbonate via the transesterification.
4
O[(O
2
C)-C
6
H
4
-
ON THE TRANSESTERIFICATION
(
2
3
Amount of the Conversion of
Yield (%)
Selectivity (%)
catalyst (%)
DMC (%)
MPC
DPC
15.9
18.22
22.9
25.7
27.2
27.7
27.5
MPC+DPC
93.7
0.2
0.4
0.6
0.8
1.0
1.2
1.4
42.7
51.6
60.2
66.7
71.2
71.6
71.5
24.3
29.8
34.4
38.5
41.7
41.5
41.6
ACKNOWLEDGEMENTS
94.6
95.2
96.3
96.7
96.9
This work was financed by the Key Projects in the National
Science & Technology Pillar Program during the Eleventh
Five-Year Plan Period (2006BAE02B03) and Yunnan
Provincial Basic & Applied Research Program (2013FZ108).
96.7
Reaction conditions: n(phenol): n(DMC) = 2, w(Zn O[(O C)-C H -
4
2
6
4
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(
CO )] ) = 1 %, time = 10 h, temperature = 160-180 C, DMC: dimethyl
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4
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10
12
14
Reaction conditions: n(phenol): n(DMC) = 2, w(Zn O[(O C)-C H -
4
2
6
4
o
(
CO )] ) = 1 %, time = 10 h, temperature = 160-180 C, DMC: dimethyl
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1
Conclusion
In summary, the advantages of this catalytic system are
that the preparation method of the catalyst is simple, fast and