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　　Synthesis of propylene glycol methyl ether over amine modified
porous silica by ultrasonic technique
Xuehong Zhang a,b, Wenyu Zhang a,b, Junping Li a, Ning Zhao a, Wei Wei a, Yuhan Sun a,*
a State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
b Graduate School of the Chinese Academy of Sciences, Beijing 100039, China
Received 16 May 2006; received in revised form 10 July 2006; accepted 12 July 2006
Available online 21 July 2006
Abstract
Amine modified porous silica were synthesized by ultrasonic technique under mild conditions. The samples, which were characterized
by BET, 29Si NMR spectra, element analysis and indicator dye adsorption, exhibited promising catalytic properties towards the synthesis
of propylene glycol methyl ether from methanol and propylene oxide. They had both high yields and reusability in the reaction, indicating
that ultrasonic technique was effective for the preparation of organically modified silica catalysts. Furthermore, the possible reaction
mechanism was proposed for the synthesis of propylene glycol methyl ether over such type of catalysts.
2006 Elsevier B.V. All rights reserved.
Keywords: Modified porous silica; Ultrasonic technique; Propylene oxide; Methanol; Propylene glycol methyl ether
1. Introduction
The attempt to heterogenize homogeneous catalyst as
alternatives to more traditional reagents and catalysts has
been one area of research that has seen increasing interest.
Much recent work was focused on the preparation of
organically modified solid bases to heterogenize homogeneous
amine catalyst. The modification process was generally
operated by stirring, heating, refluxing, etc. [1–3].
Recently, the interest in synthetic sonochemistry reactions
has grown [4]. The ultrasonic technique has been widely
applied in two-phase systems due to its advantages, such
as high accuracy and rapidity. Most of these reactions have
involved a heterogeneous chemical interaction [5]. In the
area of porous materials functionalized by organic groups,
however, only limited applications of ultrasound have been
explored [6,7]. In the present work, an alternative synthetic
route for the formation of amine modified silica was developed
by using ultrasonic energy, which can produce chemical
modifications on solids by cavitation phenomenon [8].
The amines modified silica with ‘‘single site’’ base strength
were promising catalysts for a variety of reactions [9].
The synthesis of glycol ether over base catalysts is an
important kind of reaction in organic synthesis. There are
several methods for the synthesis of propylene glycol ether
[10,11]. Among them the propylene oxide method is mostly
convenient and industrial feasible. Generally, propylene
oxide reacts with fatty alcohol via acid or base catalysis.
The catalysts used in this process include earlier homogenous
base or acid (NaOH, alcoholic sodium and BF3), later
solid acid and base. However, few studies have reported the
use of amine modified silica as catalysts for the synthesis of
propylene glycol methyl ether, though inorganic solid basic
catalysts have performed good activity in the reaction. The
immobilization of the amino functions on a mesoporous
support, which were with ‘‘single site’’ base strength, could
afford an achieving this kind of reaction.
In the present work, amine functionalized silica catalysts,
including NH2/SiO2, NH(CH2)2NH2/SiO2, TAPM/
SiO2 (2,4,6-triaminopyrimidine/SiO2) and TBD/SiO2
(1,5,7-triazabicyclo[4,4,0]dec-5-ene/SiO2), were prepared
with 3-aminopropyltrimethoxysilane (APTMS), N-[3-(tri-
methoxysilyl)propyl]ethylenediamine (EDPTMS) and 3-
chloropropyltrimethoxysilane (CPTMS) as the coupling
agents by ultrasonic technique under mild experimental
conditions. At the same time, in order to confirm the merits
of ultrasonic technique, NH2/SiO2 was also prepared by
the conventional method in order to understand the effective
behaviour of ultrasonic technique in the preparation
of functionalized porous silica. In addition, the catalytic
activity of the organic solid base catalysts was evaluated
by the synthesis of propylene glycol methyl ether from
methanol and propylene oxide. Furthermore, the possible
reaction mechanism was proposed for the synthesis of propylene
glycol methyl ether over such type of catalysts.
2. Experimental
2.1. Synthesis of catalytic materials
The amine functionalized silica catalysts could be
achieved in two ways under similar conditions as reported
earlier [7].
Aminopropylsilyl-functionalized SiO2 was prepared as
follows: 10.0 g SiO2 was preheated for 12 h at 473 K in
vacuum to remove all adsorbed moisture but surface
OH-groups, and than cooled down to room temperature
in vacuum and transferred into a 250 mL conical flask.
After mixed with 40.0 mL cyclohexane and 5.0 mL
APTMS, the mixture in conical flask was put into the ultrasonic
bath for 2 h (Sheshin, Japan, operating power 60 W)
at ambient temperature. The catalyst was then obtained by
extracting with toluene in a soxhlet extractor over a period
of 24 h and drying at 333 K in vacuum. The same method
was used for the preparation of NH(CH2)2NH2/SiO2.
TBD/SiO2 was prepared by two steps: silica was firstly
modified by 3-chloropropyltrimethoxysilane via the same
method as that of aminopropylsilyl-functionalized SiO2,
and chloropropylsilyl-functionalized SiO2 was then reacted
with TBD (1.0 g) in cyclohexane (40.0 mL). The resultant
was treated by ultrasonic vibration for 1 h. Afterwards,
the catalyst was obtained by extracting with toluene in a
Soxhlet extractor over a period of 24 h and drying at
333 K in vacuum. The same method was used for the preparation
of TAPM/SiO2.
2.2. Characterization
The content of carbon, nitrogen, and hydrogen in all the
samples was determined using a Vario EL analyzer. The
specific surface area, total pore volume and average pore
diameter were measured by N2 adsorption–desorption
method on a Micromeritics ASAP-2000 instrument (Norcross,
GA). The surface areas were calculated by BET
method, and the pore size distribution was obtained by
applying the BJH pore analysis to the nitrogen adsorption–
desorption isotherm. 29Si NMR spectra were recorded
on a Bruker MSL-400 spectrometer. The base strength of
samples was detected by hammett indicators.
2.3. Catalytic test
The catalytic properties were measured in a 75 ml batch
reactor with mol ratio of methanol and propylene oxide
being 5:1. After running at 403 K for 10 h under magnetic
stirring, the reactor was cooled down to room temperature.
The product was then filtered and analyzed by a gas chromatograph
with a flame ionization detector after centrifugal
separation from the catalysts. The catalysts were
washed with solvent and used for recycling test.
3. Results and discussion
3.1. Modification of porous silica with amine groups
The content of carbon, nitrogen, and hydrogen in
amine-free porous silica and all the modified samples were
carried out by elemental analysis. Wtorg. and Norg.% were
obtained from N%, C% and H% (see Table 1). The results
showed that there were no carbon and nitrogen in the
amine-free porous silica. As a result, carbon and nitrogen
in modified samples ought to be from the organosilanes.
The element analysis showed that Norg.% of the grafted
organic groups achieved by conventional methods known
from the literature [12] was 1.13 mmol/g, which was far
lower than that of the sample prepared by ultrasonic technique
(2.00 mmol/g) (see Table 1). This should be due to
the application of ultrasonic energy to solids and liquids,
which could provide the changes including cavitation
(bubble formation in a liquid) and chemical reaction (acceleration
of chemical reaction), etc. [13]. As a result, processes
including particle size modification, cleaning of
surfaces or the formation of fresh ones [14,15] could be
obtained in heterogeneous media at a solid liquid interface.
As to the organic modification of porous silica, cavitation
phenomena brought by ultrasound could speed up the
liquid transferring velocity in the hole of porous materials
and the liquid–solid interface. As a result, the liquid
organosilanes could be well contacted with silanol groups
on the inner wall of the porous silica to react with them
in a short time, while stiring could not reach such effect.
Therefore, the modification process finished simply and
speedily by ultrasound.
The 29Si NMR spectra in solid state indicated that the
covalent bond formed between silylant agents and silanol
groups on the silica surface (see Fig. 1). Two resonances
at 109 and 99 ppm could be attributed to 29Si nuclei
having four Si–O–Si linkages (4) and 29Si nuclei having
three Si–O–Si linkages and one OH (3) [16], respectively.
The resonances at 58 and 67 ppm were assigned
to RSi(OSi)(OH)2 and RSi(OSi)3, respectively [17], which
illustrated the successful organo functionalization of porous
silica by the organic groups via covalent bonds. C/N
value (molar ratio) could also reflect the degree of grafting
reaction between silanol groups and organosilanes [18].
NH2/SiO2, NH(CH2)2NH2/SiO2 and TBD/SiO2 showed
the C/N = 3–3.5, 2.5–3.0 and 3.3–3.6, respectively. The
results also suggested the anchorage of amine groups by
Si–O–Si bonds. This agreed with the result of the 29SiNMR spectra.
3.2. Structure and basicity of samples
Fig. 2 displays N2 adsorption isotherms for the samples
studied. The functionalized samples displayed type IV isotherms
with clear hysteresis loops associated with capillary
condensation. This indicated that the materials remained
mesoporous before and after functionalization and the
modification by various organosilanes hardly changed the
isotherm type. The BET surface area and pore volume
showed a gradual reduction as the Norg.% of grafted
organic groups increased (see Table 2). This could be
attributed to the presence of functional groups. A part of
amino groups grafted onto the microporous also led to a
decrease in the BET surface area. The effect of the organic
groups on the pore diameter of the samples was slight for
the samples NH2/SiO2 and NH(CH2)2NH2/SiO2. But as
for the sample TBD/SiO2 and TAPM/ SiO2, perhaps due
to the big framework of (CH2)3/TAPM and (CH2)3/
TBD groups, the average pore diameters of the samples
decreased to 7.90 and 8.82 nm. However, the average pore
diameter was not decreased seriously due to the low Norg.%
values of the samples.
The base strength H of a solid surface is defined as the
ability of the surface to convert an adsorbed electrically
neutral acid into its conjugate base. When an electrically
neutral acid indicator is adsorbed on a solid base from a
nonpolar solution, the color of the acid indicator is changed
to that of its conjugate base, provided that the solid
has the necessary base strength to impart electron pairs
to the acid [19]. A solid with a large positive HH has
strong basic sites. Grafting with different functional groups
could result in different base strengths. As shown in Table
3, TBD/SiO2 had the highest base strength of H 15.0,
while NH2/SiO2 and NH(CH2)2NH2/SiO2 only had the
basicity of H 9.3 and 9.3 < H < 15.0, respectively.
Compared to the other modified samples, TAPM/SiO2
had weakest basicity of H < 7.2. Thus, the basic strength
of the samples was in the order of TBD/
SiO2 > NH(CH2)2NH2/SiO2 > NH2/SiO2 > TAPM/SiO2.
3.3. Catalytic performance
The catalytic activity was tested in the synthesis of propylene
glycol methyl ether from methanol and propylene
oxide (see Table 3). As shown in Table 3, PO conversion
and isomer selectivity (the ratio of 1-methoxy-2-propanol/
total propylene glycol methyl ether) reached 27.3 and
72.3% without the presented catalysts, respectively. Among
the catalysts, the amine-free porous silica showed the low
catalytic activity due to the weak acid strength of the surface
silanol groups. For anchored amino groups
NH(CH2)2NH2/SiO2 and NH2/SiO2 catalysts were found
to be more active and selective than other catalysts to 1-
methoxy-2-propanol after 10 h of reaction. TAPM/SiO2
catalyst had low propylene oxide conversion (89.0%) with
the isomer selectivity of 66.6%. TBD/SiO2,
NH(CH2)2NH2/SiO2 and NH2/SiO2 catalysts all showed
high propylene oxide conversion (>94%), but different isomer
isomer
selectivity. NH(CH2)2NH2/SiO2 and NH2/SiO2 with
weaker base strength had higher isomer selectivity
(>82%), while TBD/SiO2 with moderate base strength
showed lower isomer selectivity (73.7%). As for solid base
catalysts, catalysts with moderate base strength should
have good isomer selectivity [20]. The lower isomer selectivity
of TBD/SiO2 could be due to the big framework of
TBD.
The catalysts were easily recovered by filtration, and
subjected to utilization for seven cycles with constant conversion
of propylene oxide >89% and the utilization for
many recycles hardly changed the isomer selectivity under
403 K (see Table 4), indicating that amine groups grafted
onto silica surface were stable under the experimental conditions.
The reusability of other samples was similar to that
of NH2/SiO2.
3.4. Possible mechanism
Inorganic solid base catalysts have been extensively used
for the synthesis of propylene glycol methyl ether from
methanol and propylene oxide [31], in which, the methoxide
ion and proton was absorbed on acidic and basic sites
on the catalyst surface, respectively, and then the methoxide
ion attacked the C(1) position. In the present case, however,
the samples used for the reaction were characteristic
of single site, i.e., the catalyst with unique basic site similar
to the homogeneous base. Because there was no Lewis
acidic site on the catalysts, the mechanism should be different
from those involving bifunctional catalysts. The plausible
mechanism of 1-methoxy-2-propanol formation on
NH2/SiO2 is illustrated in Scheme 1. There was H-bonds
O atom in methanol attacked the C(1) position and proton
was absorbed on the basic sites of the catalysts, and then
C(1)–O band cracked, followed by pick up the proton to
form 1-methoxy-2-propanol.
It seems reasonable to consider that the higher activity
of NH(CH2)2NH2/SiO2, NH2/SiO2 and TBD/SiO2 was
due to the appropriate base strength, which could not only
form H-bond but also crack it easily. TAPM/SiO2 with
very weak base strength could only form more unstable
H-bond. Thus, the activity of TAPM/SiO2 was lower than
the other samples. On condition that such mechanism is
reasonable, the big framework of the organic groups probably
could affect the attacking position of the O atom in
methanol. As a result, TBD of the big framework led to
lower isomer selectivity. Thus, both appropriate base
strength and simple framework of the organic groups were
important for the high conversion and good selectivity to
1-methoxy-2-propanol.
4. Conclusions
The results presented above led to the following conclusions:
(1) the efficient ultrasonic technique could successfully
prepare the amine functionalized porous silica
catalysts, (2) the characterization indicated that the amine
groups were grafted onto the silica surface by covalent
bond, (3) appropriate base strength and simple framework
of the organic groups were important for the high conversion
and good selectivity to 1-methoxy-2-propanol, (4) the
catalysts could be recovered by filtration and were subjected
to utilization for many cycles with constant activity.

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