Study on the transesterification and mechanism of bisphenol A and dimethyl carbonate catalyzed by organotin oxide

Article abstract of DOI:10.1007/s11696-019-00759-0

(CF₃C₆H₄)₂SnO, (CH₃C₆H₄)₂SnO and Ph₂SnO were successfully synthesized for the transesterification of DMC with BPA. The products of mono-methylcarbonate-ended-BPA (MmC(1)) and two-methylcarbonate-ended-BPA (DmC(1)) were selectively synthesizedthem. The catalysts were characterized by FT-IR, TG and XPS. When Ph₂SnO was used as the catalyst at 170?°C, the BPA conversion reached to 28.60% and the transesterification selectivity reached to 98.35%. As for (CF₃C₆H₄)₂SnO, BPA conversion and transesterification selectivity declined to 12.48% and 64.74%, respectively. The BPA conversion increased to 42.83%, but the transesterification selectivity declined to 44.55%(CF₃C₆H₄)₂SnO. Notability, the higher transesterification selectivity of Ph₂SnO was due to its lowest electron binding energy of Sn⁴⁺. More importantly, the DMC adsorption, activation and decomposition process(CF₃C₆H₄)₂SnO, (CH₃C₆H₄)₂SnO and Ph₂SnO were characterized by TG–MS and in situ DRIFT techniques, which provided more information about the mechanism of transesterification and methylation.

Full text of DOI:10.1007/s11696-019-00759-0

Chemical Papers (2019) 73:2171–2182
https://doi.org/10.1007/s11696-019-00759-0
ORIGINAL PAPER
Study on the transesterifcation and mechanism oꢀ bisphenol
A and dimethyl carbonate catalyzed by organotin oxide
1
2
1
1
1
Yanan Liang · Kunmei Su · Lei Cao · Yuan Gao · Zhenhuan Li
Received: 26 September 2018 / Accepted: 25 March 2019 / Published online: 22 April 2019
Institute of Chemistry, Slovak Academy of Sciences 2019
©
Abstract
(
CF C H ) SnO, (CH C H ) SnO and Ph SnO were successfully synthesized for the transesteriꢀcation of DMC with BPA.
3 6 4 2 3 6 4 2 2
The products of mono-methylcarbonate-ended-BPA (MmC(1)) and two-methylcarbonate-ended-BPA (DmC(1)) were selec-
tively synthesized over them. The catalysts were characterized by FT-IR, TG and XPS. When Ph SnO was used as the
2
catalyst at 170 °C, the BPA conversion reached to 28.60% and the transesteriꢀcation selectivity reached to 98.35%. As for
(
CF C H ) SnO, BPA conversion and transesteriꢀcation selectivity declined to 12.48% and 64.74%, respectively. The BPA
3 6 4 2
conversion increased to 42.83%, but the transesteriꢀcation selectivity declined to 44.55% over (CF C H ) SnO. Notability,
3
6
4 2
4
+
the higher transesteriꢀcation selectivity of Ph SnO was due to its lowest electron binding energy of Sn . More importantly,
2
the DMC adsorption, activation and decomposition process over (CF C H ) SnO, (CH C H ) SnO and Ph SnO were char-
3
6
4 2
3
6
4 2
2
acterized by TG–MS and in situ DRIFT techniques, which provided more information about the mechanism of transesteri-
ꢀ
cation and methylation.
Keywords Bisphenol A · Dimethyl carbonate · Phenyl tin oxide catalysts · TG–MS · In situ DRIFT
Introduction
Lee 2010; Kim et al. 1992; Kim and Choi 1993; Turska
and Wróbel 1970), CO (Goyal et al. 1999a, b; Hallgren and
Lucas 1981; Ishii et al. 2000; Moiseev et al. 1996; Song et al.
2000; Takagi et al. 1998), and DMC (Bolon and Hallgren
1984; Deshpande et al. 1995; Haba et al. 2015; Pokharkar
and Sivaram 1995; Shaikh et al. 1994) were used as carbon-
ylation agents to replace phosgene. The synthesis of PC by
oxidative carbonylation of BPA with CO requires expensive
noble metal palladium as a catalyst; this method of prepar-
ing PC is diꢁcult to industrialize because the low average
molecular weight of PC produced can be obtained (Goyal
et al. 1999a, b, 2000; Wang et al. 2004). High-molecular
weight PC can be obtained by melting polycondensation of
DPC with BPA, but the obtained byproduct phenol can only
be removed in high temperature (higher than 300 °C) and
low vacuum (less than 13 Pa). Furthermore, the high tem-
perature always leads to more side reactions, which resulted
in the discoloration of the PC resin (Schnell 1964). DMC
can react with BPA to prepare precursor of polycarbonate.
The catalyst used in this method is cheaper than the oxida-
tive carbonylation of carbon monoxide. Moreover, DMC is
completely qualiꢀed for a green reagent, and the byproduct
methanol can be easily removed at low temperature (Huang
et al. 2015). It is reported that high-molecular weight PC
PC is the fastest growing general engineering plastic among
the ꢀve engineering plastics (Artham and Doble 2008). It
is usually prepared through interfacial polycondensation of
phosgene and bisphenol A (BPA). However, a large amount
of toxic phosgene and methylene chloride was used as raw
material and solvent in this method uses a large amount of
toxic phosgene and methylene chloride as raw material and
solvent. (Fukuoka et al.2003). To avoid the use of highly
toxic reagents in the preparation of PC, diphenyl carbonate
(
DPC) (Fukuoka et al. 2003; Curtius et al. 1969; Kim and
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s11696-019-00759-0) contains
supplementary material, which is available to authorized users.
*
Zhenhuan Li
lizhenhuan@tjpu.edu.cn; ZhenhuanLi1975@yahoo.com.cn
1
State Key Laboratory of Separation Membranes
and Membrane Processes, School of Materials, Science
and Engineering, Tianjin Polytechnic University,
Tianjin 300387, China
2
School of Environment Science and Chemistry Engineering,
Tianjin Polytechnic University, Tianjin 300387, China
Vol.:(0
1
123456789)
3

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Chemical Papers (2019) 73:2171–2182
can be obtained by melt-polycondensation of two-methyl
carbonate-ended oligomers (DmC (1)) or one-methylcarbon-
ate-ended-BPA (MmC (1)) (Haba et al. 2015; Shaikh et al.
Catalyst preparation
Ph SnO was synthesized as the following steps. The syn-
2
1
994). Therefore, the transesteriꢀcation of BPA with DMC
thesis of Grignard reagents was performed in a three-neck
ꢂask equipped with a thermometer, dropping funnel and
a reꢂux condensing tube. Magnesium ribbon (2.4 g) and
anhydrous ether (150 mL) were charged into ꢂask under
nitrogen atmosphere. When the temperature increased to
40 °C, the ether solution of bromobenzene (15.7 g) began
to drop slowly, and after at least 2 h, the Goliath reagent
was obtained.
is particularly important for the synthesis of DmC (1). Kim
and Lee (2010) investigated the activity of TiO /SiO with
2
2
small speciꢀc surface area and they found that the conver-
sion of BPA was only reached to 11% within 55 h at the
reaction temperature of 160 °C, and the yield of MmC(1)
was only 10%. Su et al. (2010) synthesized TiO /SBA-15
2
to catalyze the transesteriꢀcation of DMC with BPA. It was
found that the conversion of BPA reached to 30.33%; the
yield of DmC(1) and MmC(1) achieved 25.3% and 3.6%
under the optimized conditions, respectively. Organotin
oxide has been widely used in catalytic transesteriꢀcation
Stannic tetrachloride (5.85 mL) and toluene (50 mL)
were charged into ꢂask under nitrogen atmosphere. The
Goliath reagent was slowly dripped at 110 °C. The ether
was removed after 3 h of reaction. The rest of mixture was
transferred into a PTFE-lined reactor to continue reacting
for 4 h at 150 °C. After the reactor cooled down, the ꢀl-
tered ꢀltrate was precipitated by NaOH (1 mol/L), and the
solid was reꢂuxed in NaOH for 2 h. The solid was washed
to neutral by deionized water and dried in vacuum oven at
(
Shaikh and Sivaram 1996). Li et al. (2011) grafted organo-
tin oxide onto SBA-15 molecular sieve for transesteriꢀca-
tion of BPA and DMC, but the yield of DmC (1) and MmC
(
1) was still very low compared with (C H ) SnO. Liang
4 9 4
et al. (2019) catalyzed the transesteriꢀcation of DMC and
BPA with lithium-doped titanium dioxide, but the selectiv-
ity of alkylation was still unsatisfactory. Haba et al. (2015)
reported that DmC(1) could be synthesized by transesteriꢀ-
cation of BPA with excess DMC. They found that the yield
of DmC(1) reached 22% over (Bu SnCl) O/DMAP, but a
120 °C for 12 h to obtain Ph SnO. The preparation process
2
of (CF C H ) SnO and (CH C H ) SnO (see supporting
3
6
4 2
3
6
4 2
information) is detailed.
2
2
large amount of 4 A molecular sieve was added to remove
byproduct methanol. Furthermore, it was found that alkyltin
oxide, such as (C H ) SnO, (C H ) SnO, and (PhCH ) Sn
Characterization
Fourier-transform infrared spectroscopy of catalysts was
measured by KBr Compression method with BRUKER
FT-IR Analyzer. The surface chemical information and
elemental analysis of the catalysts were characterized
by X-ray photoelectron spectroscopy (XPS) with Mg kα
(1253.6 e V) X-ray source from Thermo Fisher Com-
pany, USA. The samples of 2–8 mg were put into TG
(STA449F3, Netzsch Instruments) crucible, volatilized
or decomposed under temperature-programmed condi-
tions, and detected by MS (QMS403C, Netzsch Instru-
ments) detector. The heating rate was 2 °C/min and the
carrier gas was high-purity nitrogen with ꢂow velocity of
60 mL/min. In situ infrared spectra were obtained by dif-
fuse reꢂectance instrument with Nicolet 6700 detector. In
addition, in situ DRIFT spectra were collected on a Nico-
let 6700 spectrometer supplied with a diꢃuse reꢂectance
attachment. The catalysts were put into the PIKE DRIFT
reaction cell which could work under high temperature and
4
9 2
6
11 2
2 2
exhibited higher BPA conversion but lower DmC(1) selec-
tivity in our previous work (He et al. 2013).
In this work, (CF C H ) SnO, (CH C H ) SnO and
3
6
4 2
3
6
4 2
Ph SnO were successfully synthesized and characterized by
2
various techniques, and the transesteriꢀcation of DMC with
BPA was carried out over them. It was found that Ph SnO
2
displayed the outstanding catalytic performance in the trans-
esteriꢀcation, and the transesteriꢀcation selectively reached
9
8.35%. The adsorption–activation–desorption mechanism
of DMC on Ph SnO was characterized by TG–MS and
2
in situ drift, and the suitable mechanism of transesteriꢀca-
tion between DMC and BPA was proposed.
Experimental
Chemical reagents
high pressure. Ph SnO was treated at 200 °C with high-
2
Dimethyl carbonate (DMC) (99.9 wt%) was purchased from
Macklin Biochemical Co., Ltd., Shanghai, China. BPA
purity Ar for 0.5 h before entering DMC, then cooled to
room temperature to test the background of the sample.
Subsequently, the catalyst kept adsorbing DMC at room
(
(
Tianjin Chemical Reagent Co. (III)) was analytic reagent
AR) grade and used without further puriꢀcation.
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3

Chemical Papers (2019) 73:2171–2182
2173
temperature until the spectrum of the signal was constant.
The spectra were collected under diꢃerent backgrounds
of mirror and sample, respectively. When the catalyst was
saturated with DMC, argon was injected to remove excess
DMC. In situ adsorption spectra were measured with the
desorption of DMC as temperature increased and obtained
in mirror background and sample background.
reheated to 170 °C under rigorous stirring, DMC was added
drop-wise by a controlled volume pump and the feeding rate
of DMC during the reaction is 30 μL/min. During the reac-
tion, the mixture of DMC and methanol was collected slowly
in a receiver ꢂask. After reaction, mixture was cooled and
analyzed by GC–MS. The products were mainly one-methyl-
carbonate-ended-BPA (MmC(1)) and two-methylcarbonate-
ended-BPA (DmC(1)), O-methylation of BPA (A), and from
ortho-methylation of BPA with DMC (B and C) (Scheme 1).
The selectivity of products to MmC(1) and DmC(1) was
deꢀned as the moles of MmC(1) and DmC(1) produced per
100 mol of consumed BPA.
Reaction procedure
The interaction of Ph SnO with DMC was performed in a
2
three-neck ꢂask, equipped with a thermometer and a reꢂux
condensing tube. 0.5 g catalyst and 70 mL DMC were loaded
into the ꢂask. The interaction lasted for 10 h at 90 °C to
(
initial moles of BPA − final moles of BPA) ∗ 100
Conversion % =
,
inital moles of BPA
guarantee DMC was saturated and adsorbed by Ph SnO.
2
(1)
After that, Ph SnO/DMC was air-dried for 24 h and then
2
(
moles of product formed) ∗ 100
tested by TG–MS.
Selectivity of products % =
,
moles of BPA reacted
Transesteriꢀcation was carried out in a three-neck ꢂask,
equipped with a thermometer, a controlled volume pump
and fractionating column connected to a liquid dividing head
under atmospheric pressure. BPA and catalyst were charged
into ꢂask under nitrogen atmosphere. When the mixture was
(
(
2)
Yield % = conversion of BPA*selectivity of products.
3)
Scheme 1 The main products of reaction between BPA and DMC
Fig. 1 a FT-IR spectra of phenyl tin oxide catalysts, b TG of phenyl tin oxide catalysts
1
3

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Chemical Papers (2019) 73:2171–2182
Fig. 2 The full scan (a) and Sn 3d (b) XPS of phenyl tin oxide catalysts
Results and discussion
observed for (CF3C6H4)2SnO, which was in agreement with
the above FT-IR results. Figure 2b reveals Sn 3d peaks of
phenyl tin oxide catalysts. Sn 3d peaks of (CF3C6H4)2SnO
appeared at 496 eV and 487.6 eV, which were higher than
those of (CH3C6H4)2SnO and Ph2SnO. Sn 3d electron bind-
ing energy of Ph2SnO was the lowest among the three phe-
nyl tin oxide catalysts. It indicated that Sn cation activity
among the three phenyl tin oxide catalysts was as follows:
(CF3C6H4)2SnO>(CH3C6H4)2SnO>Ph2SnO (Xia et al.
2014).
Catalyst characterization
Figure 1a shows the FT-IR spectrum of the catalyst. The
−
1
absorption peak near 1600 cm was mainly attributed to
the stretching vibration of the benzene ring skeleton. The IR
−
1
peak at 750 cm for (CH C H ) SnO and (CF C H ) SnO
3
6
4 2
3
6
4 2
was assigned to P-substituted of the benzene ring. The
−
1
IR bands appeared at 1172 cm were ascribed to Sn=O
bond stretching vibration, which was in agreement with
the published results (He et al. 2013). At the same times,
Adsorption–activation–desorption mechanism
−
1
−1
two weak bands located at 2920 cm and 2855 cm for
(
CH C H ) SnO were mainly attributed to the presence of
The diꢃerent active sites of DMC on the surface of Ph2SnO
were characterized by TG–MS techniques. The appearance
of DMC (Fig. 3a) and CH3OH (Fig. 3b) was observed in
TG–MS curves of DMC–Ph2SnO. The desorption or decom-
position signals of the adsorbed DMC were detected at about
68, 87, 132, 156 and 170 °C, respectively. The desorption
signals at 68–87 °C were attributed to the physical and weak
chemisorption of DMC on the Ph2SnO surface. The desorp-
tion or decomposition signals at 132, 156 and 170 °C indi-
cated the formation of diꢃerent adsorption types of DMC
on the surface of the catalyst at high temperature. (Gao
et al. 2016). The escapement peak of methanol was also
detected in the TG–MS curves, due to the decomposition of
DMC at high temperatures (Raab et al. 2001; Vilela et al.
2010). According to the results of TG–MS, ꢀve temperature
points of 68, 87, 132, 156 and 170 °C were selected, and the
adsorption types of DMC were determined by in situ drift.
The mechanism of adsorption–activation–desorption
of DMC on Ph2SnO surface was characterized by in situ
DRIFT. Figure 4a and c shows in situ infrared spectra of
DMC adsorbed on Ph2SnO at selected temperatures under
mirror background and sample background, respectively.
3
6
4 2
−1
–
CH Additionally, the IR bands that appeared at 1300 cm
3.
for (CF C H ) SnO were due to the asymmetric stretch of
3
6
4 2
the C–F bond. Figure 1b shows TG curves of diꢃerent cata-
lysts. The weights of (CH C H ) SnO, (CF C H ) SnO and
3
6
4 2
3
6
4 2
Ph SnO remained almost constant up to 200 °C. The decom-
2
position of phenyl tin oxide occurred at about 200 °C, which
was much higher than the transesteriꢀcation temperature. In
a wide temperature range of 200–550 °C, the catalyst weight
residual was 51.8%, 41.2% and 55.5% for (CH C H ) SnO,
3
6
4 2
(
CF C H ) SnO and Ph SnO, respectively. These results
3 6 4 2 2
were attributed to the decomposition of organic groups. The
results of the experiment were very close to the theoretical
values 47.5%, 37.4% and 51.9%, respectively. Above 550 °C,
the weight loss was attributed to the decomposition of oxides
of Sn (Song et al. 2011).
The surface chemical state of solid catalyst could be
detected by XPS (Jing et al. 2003). Figure 2 indicates the
full scan and the high-resolution XPS spectra of phenyl
tin oxide. The results of full spectrum scanning analysis
of XPS demonstrated that the elements of O, C, Sn could
be detected in all samples (Fig. 2a). But only F could be
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Chemical Papers (2019) 73:2171–2182
2175
Fig. 3 TG–MS curves of DMC–Ph SnO: a DMC, b CH OH
2
3
The characteristic absorption peak at 3054 cm−1 was attrib-
uted to the stretching vibration of C–H on the benzene,
loading, etc.). The stretching vibrational peaks of methyl
−
1
in liquid DMC appeared at 2962 and 2852 cm (Fig. 4d.).
However, the methyl peak appeared and shifted to 2904 and
−
1
while the peak at 1072 cm was caused by the stretching
vibration of the Sn=O bond. In addition, the absorption
−
1
2825 cm when the temperature was higher than 156 °C,
which further indicated that high temperature led to methyl
activation to form alkylation products.
−
1
−1
peaks at 1293 cm and 1765 cm were attributed to the
stretching vibration of O–C–O and C=O bonds, respectively.
With the increase of temperature from 68 to 170 °C, the
stretching vibration peaks of O–C–O and C=O split into
Figure 5 shows the corresponding MS curves of
(CH C H ) SnO. It was observed that there were a large
3
6
4 2
−
1
−1
1
305–1263 cm and 1800–1764 cm , respectively. That
number of DMC and CH OH escape before 200 °C. There
3
was attributed to the conformation of diꢃerent DMC adsorp-
are ꢀve desorption temperature points for DMC: 71 °C,
108 °C, 121 °C, 142 °C, 175 °C. The adsorption type could
be further determined by situ DRIFT and the product distri-
bution between BPA and DMC at these temperature points
could be detected by GC.
tion types on the surface of Ph SnO [cis–cis (I)and cis–trans
2
(
II) and cis–cis species III (Scheme 2)]. The positive charge
of the carbonyl carbon atom increased because the Sn atom
in Sn=O interacted with the carbonyl oxygen atom, which
−
1
leads to the red shift of C=O (1764 cm ) and the blue shift
The in situ DRIFT spectra of DMC adsorbed on
(CH C H ) SnO at various temperatures in mirror back-
−
1
of O–C–O (1305 cm ). After that, hydroxyl oxygen atoms
in BPA reacted with carbonyl carbon atoms to form trans-
esteriꢀcation products. The intensity of the blue shift peak
3
6
4 2
ground are shown in Fig. 6a. The absorption band at
−
1
1765 cm was caused by stretching vibration of C=O
bond, but it could not obtain more information as tem-
−
1
at 1800 cm increased with the temperature rose, (Fig. 4b),
which was attributed to the interaction of the Sn atom in
Sn=O bond with the methyl oxygen atom. Meanwhile, the
−
1
perature rises near 1765 cm . Therefore, in situ DRIFT of
DMC adsorbed on (CH C H ) SnO at various temperatures
3
6
4 2
positive charge of the carbon atom in the CH3O increased.
in sample background is shown in Fig. 6b. The position of
υ(C=O) almost unchanged when the temperature rises to
71 °C, 108 °C and 121 °C, while the peak splits into two
−
Moreover, the negative peak of CH O was measured, which
3
indicated that the interaction of carbonyl oxygen with Sn
−
1
−1
weakened the bond energy of O–CH in DMC. Oxygen
major components at 1774 cm and 1744 cm as tem-
perature increases to 142 °C and 175 °C (Fig. 6c). The blue-
3
atoms in BPA mainly reacted with the methyl of DMC to
form alkylation products (Scheme 1). Therefore, the coordi-
nation between carbonyl oxygen atoms and Sn resulted in the
−
1
shifted peak at 1774 cm was stronger than the red-shifted
−
1
peak at 1744 cm , suggesting methylation products were
easier to form with the catalysis of (CH C H ) SnO. In addi-
activation of the carbonyl group and the O–CH moieties of
3
3
6
4 2
−
1
the organic carbonate (Bonino et al. 2005; Distaso and Quar-
tion, stretching vibration of –CH appearing at 2863 cm
3
−
anta 2008). The degree of activation of CH O increased as
implies that methylation activities were obvious at 153 °C
and 175 °C.
3
the temperature increases (Fig. 4c). An experimental sup-
porting evidence is presented in Table 2, which compared
the eꢃect of the temperature on the reactivity of DMC under
The TG–MS curves of (CF C H ) SnO are shown in
3
6
4 2
Fig. 7. As shown in Fig. 7, the desorption of a small amount
otherwise analogous reaction conditions (time, Ph SnO
of DMC probably comes from physical adsorption or weak
2
1
3

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Chemical Papers (2019) 73:2171–2182
Fig. 4 a In situ DRIFT spectra of DMC adsorbed on Ph SnO at various temperatures in mirror background, b corresponding magniꢀcation of
2
selected area. c In situ DRIFT spectra of DMC adsorbed on Ph SnO at various temperatures in a sample background, d FT-IR spectra of DMC
2
chemisorption before 140 °C. Temperature above 140 °C
may be attributed to chemisorption. Therefore, the three
temperature points at 74 °C, 135 °C, and 168 °C were
selected to analyze DMC adsorption type by in situ DRIFT
and then to catalyze BPA and DMC to determine the com-
position of its product by GC.
In situ DRIFT spectra of DMC adsorbed on
(
CF C H ) SnO at various temperatures in mirror back-
3 6 4 2
Scheme 2 DMC absorbs over phenyl tin oxide (Cis–cis species I,
Cis–trans species II, Cis–cis species III)
ground and sample background are presented in Fig. 8. The
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3

Chemical Papers (2019) 73:2171–2182
2177
Fig. 5 TG–MS curves of DMC–(CH C H ) SnO: a DMC, b CH OH
3
6
4 2
3
stretching vibration at 2855 cm−1 was caused by CH - of
The eꢃects of diꢃerent reaction temperatures on the cat-
3
DMC which becomes clear at 165 °C; it was indicated that
methylation activity was obvious at this temperature (Table 4
entry 3). Therefore, the higher temperature, the more meth-
ylated product. From 74 to 165 °C, the peak shape changed
from positive to negative, which illustrated methylation that
activity at 96 °C and 165 °C was diꢃerent from 74 °C. The
alytic activity of Ph SnO were tested, and the results are
2
listed in Table 2. The reaction temperature was varied from
68 to 170 °C, and BPA conversion increased from 0.2 to
28.60%, while transesteriꢀcation selectivity decreased from
100 to 98.35%, and only 1.65% methylation products were
detected. In addition, based on the in situ DRIFT, TG–MS
and FT-IR characterization, high temperature might destroy
the adsorption type of cis–cis species (I) or cis–trans spe-
cies (II), which also results in the increase of methylated
products.
−
1
negative peaks of O–C–O move to 1275 cm under 96 °C
and 165 °C, but the peak at 74 °C was still positive, which
indicates the diꢃerence between chemisorption at 165 °C
and physisorption at 74 °C.
Table 3 shows the catalytic activity of (CH C H ) SnO
3
6
4 2
at diꢃerent reaction temperatures. It can be seen from the
results that the transesteriꢀcation selectivity was 100 when
the reaction temperature was lower than 121 °C. When
the reaction temperature was 175 °C, the conversion of
BPA increased 60.49%, but the selectivity of methylation
increased sharply to 88.13%, and the selectivity of trans-
esterification decreased to 11.87%. None DmC(1) was
detected.
Catalytic activity
(
CF C H ) SnO, Ph SnO and (CH C H ) SnO were used as
3 6 4 2 2 3 6 4 2
catalysts to test transesteriꢀcation between BPA and DMC,
and the results are shown in Table 1. Ph SnO exhibited the
2
best performance for transesteriꢀcation, BPA conversion
achieved 28.60%, and transesteriꢀcation selectivity [MmC
(
1) and DmC (1)] was 98.35%. When (CF C H ) SnO
The eꢃect of reaction temperature on the catalytic activ-
ity of (CF C H ) SnO is listed in Table 4. According to the
3
6
4 2
was used as catalyst, the BPA conversion and methylation
selectivity increased to 42.83% and 55.4%, respectively.
But the transesteriꢀcation selectivity decreased to 44.6%.
Besides, the methylation selectivity and the conversion of
BPA declined to 35.26% and 12.48% over (CH C H ) SnO.
3
6
4 2
selected temperature, the conversion of BPA increases from
0 to 40.92%, and the selectivity of transesteriꢀcation was
93.43% when the reaction temperature was 132 °C. How-
ever, when the reaction temperature was 165 °C, the trans-
esteriꢀcation selectivity decreased to 46.6 °C.
3
6
4 2
Based on the above discussion results, the lower activity
of (CF C H ) SnO in transesterification was caused by
Figure 9 shows the eꢃects of the amount of Ph SnO on
3
6
4 2
2
the stronger electron withdraw which came from the trif-
the transesteriꢀcation of DMC and BPA. When the amount
luoromethyl benzene group (see XPS analysis). The high
of Ph SnO was 0.05 g, the yields of MmC(1) and DmC(1)
2
transesteriꢀcation selectivity of Ph SnO may be related to
were 14.3% and 1.31%. As the amount of catalyst increased
to 0.25 g, the yields of MmC(1) and DmC(1) increased
to 25.8% and 2.3%, respectively. Meanwhile, methylation
2
its conꢀned region eꢃects (see Supporting information) (Li
et al. 2011).
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3

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Chemical Papers (2019) 73:2171–2182
Fig. 6 a In situ DRIFT spectra of DMC adsorbed on (CH C H ) SnO at various temperatures in a mirror background, b Corresponding magniꢀ-
3
6
4 2
cation of selected area. c In situ DRIFT spectra of DMC adsorbed on (CH C H ) SnO at various temperatures in sample background
3
6
4 2
selectivity reached to the minimum of 1.65%. When the
catalyst amount was 0.4 g, MmC(1) and DmC(1) yields
decreased to 15.28% and 1.06%, while the methylation
selectivity increased to 7.64%. The excessive catalyst could
lead to the decarboxylation of MmC(1) and DmC(1) (Bae
Suggested mechanism
The plausible mechanism of the carboxymethylation of
DMC with BPA over Ph SnO catalyst is shown in Scheme 3.
2
When the transesteriꢀcation of DMC with BPA was cat-
2
0
015Query). Therefore, the optimal catalyst amount was
.25 g.
alyzed by Ph SnO, the interaction between Sn cations in
2
1
3

Chemical Papers (2019) 73:2171–2182
2179
Fig. 7 TG–MS curves of DMC–(CF C H ) SnO: a DMC, b CH OH
3
6
4 2
3
Fig. 8 a In situ DRIFT spectra of DMC adsorbed on (CF C H ) SnO at various temperatures in mirror background, b in situ DRIFT spectra of
3
6
4 2
DMC adsorbed on (CF C H ) SnO at various temperatures in sample background
3
6
4 2
Table 2 The eꢃects of Ph SnO on the selective carboxylation of BPA
2
with DMC in diꢃerent temperatures
Table 1 The eꢃects of diꢃerent phenyl tin oxide catalysts on the
Catalyst Tem-
perature
°C)
Conversion (%) Selectivity distribution (mol
%)
selective carboxylation of BPA with DMC at the same temperature
(
Catalyst
Conversion (%) Selectivity distribution (mol %)
Methyl MmC (1) DmC (1)
Methyl MmC (1) DmC (1)
Ph SnO 68
0.2
0
100
0
2
8
7
1.71
8.04
14.03
28.60
0
0
0.83
1.65
100
100
99.17
90.33
0
0
0
8.02
(
55.40
1.65
35.26
41.34
90.33
63.57
3.26
8.02
1.17
3
6
4 2
130
156
170
Ph SnO
(
CH C H ) SnO 12.48
Reaction conditions: BPA 2.28 g, DMC 17 mL, catalyst 0.25 g, T
70 °C, t 10 h
1
Reaction conditions: BPA 2.28 g, DMC 17 mL, catalyst 0.25 g, t 10 h
1
3

2180
Chemical Papers (2019) 73:2171–2182
Table 3 The eꢃects of
Catalyst
Temperature
Conversion (%)
Selectivity distribution (mol %)
(
CH C H ) SnO on the
3 6 4 2
(
°C)
selective carboxylation of
BPA with DMC in diꢃerent
temperatures
Methyl
MmC (1)
DmC (1)
(CH3C6H4)2SnO
71
0.16
1.77
3.59
10.35
60.49
0
0
100
100
0
0
0
1.75
0
1
1
1
1
08
21
42
75
0
100
65.78
11.87
32.47
88.13
Condition: BPA 2.28 g, DMC 17 mL, catalyst 0.25 g, 10 h
Table 4 The eꢃects of
Catalyst
Temperature
Conversion (%)
Selectivity distribution (mol %)
(
CH C H ) SnO on the
3 6 4 2
(
°C)
selective carboxylation of
BPA with DMC in diꢃerent
temperatures
Methyl
MmC (1)
DmC (1)
(CF3C6H4)2SnO
74
0
12
40.92
0
0
0
1
32
65
6.57
53.40
82.67
45.34
10.75
1.26
1
Condition: BPA 2.28 g, DMC 17 mL, catalyst 0.25 g, 10 h
Fig. 9 Eꢃect of Ph SnO amount on transesteriꢀcation of BPA with DMC (reaction conditions: BPA 2.28 g, DMC 17 mL, T 170 °C, t 10 h)
2
Sn=O and O atoms in C=O increased the positive electrical
of carbonyl carbon atoms to form the type of cis–cis spe-
cies (III) adsorption. At the same time, hydrogen atoms of
BPA reacted with oxygen atoms in Sn=O to form hydrogen
bonds. Carbonyl carbon of DMC was attacked by hydroxyl
oxygen in BPA to form transesteriꢀcation products.
came up to 98.35%. The blue-shift peak of in situ DRIFT
−
1
spectra at 1800 cm indicated that the oxygen atoms pro-
vided by CH –O of DMC combined with Sn in Sn=O to
3
form cis–cis species (I) or cis–trans species (II), and this
process was accompanied by the formation of methylation
products. When Sn in Sn=O interacted with the oxygen of
the C=O to form cis–trans species (III), the oxygen of BPA
attacked the carbonyl carbon to form carboxymethylation
Conclusion
Ph SnO showed the best catalytic performance in the reac-
2
tion of BPA with DMC at 170 °C, the conversion of BPA
reached 28.6%, and the selectivity of transesteriꢀcation
1
3

Chemical Papers (2019) 73:2171–2182
2181
Scheme 3 The plausible mechanism of the carboxymethylation of DMC with BPA over Ph SnO catalyst
2
products, resulting in red-shift υ (C=O) at 1746 cm−1 on the
in situ DRIFT spectra. In addition, regional eꢃects can also
aꢃect the selectivity of ester exchange reactions.
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tion of aliphatic amines with dimethyl carbonate (DMC): DMC
activation by η1-O(C=O) coordination to Sc(III) and its relevance
to catalysis. J Catal 253:278–288. https://doi.org/10.1016/j.
jcat.2007.11.004
Acknowledgements The authors are grateful for the ꢀnancial support
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