Applied Catalysis A: General 294 (2005) 188196

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The mechanism for the synthesis of 1-methoxy-2-propanol from

methanol and propylene oxide over magnesium oxide
Wenyu Zhang a,b, Hui Wang a,b, Qibiao Li a,b, Qingnian Dong 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, PR China
b
Graduate School of Chinese Academy of Sciences, PR China
Received 7 January 2005; received in revised form 4 July 2005; accepted 11 July 2005

Abstract

The addition of propylene oxide with methanol was carried out over solid bases and a detailed mechanism of the reaction over MgO was
investigated by using FT-IR method. It was found that 1-methoxy-2-propanol could be selectively synthesized on MgO, which had base sites
of moderate strength, while CaO and Al2O3 showed either low activity or selectivity toward the production of 1-methoxy-2-propanol. In situ
FT-IR revealed that methanol dissociation into methoxide and proton took place readily on MgO, and that propylene oxide adsorbed on MgO
could generate propylene-like species via carbanion intermediates. As a result, methanol dissociated into adsorbed methoxide and reacted
with the propylene-like specie in anti-Markownikov fashion, which led to the high selectivity to 1-methoxy-2-propanol on MgO.
# 2005 Elsevier B.V. All rights reserved.

Keywords: 1-methoxy-2-propanol; FT-IR; CO2-TPD; MgO

1. Introduction

Glycol ether is a fine chemical that is widely used as an

industrial solvent for coating material and printing inks.
Because of the negligible toxicity, propylene glycol ether is
expected to be a safe substitute for toxic ethylene glycol ether
[1]. Among the methods developed for the synthesis of
propylene glycol ether [24], the propylene oxide routewas the
most convenient and the most industrially feasible. Generally,
propylene oxide reacts with a fatty alcohol via acid or base
catalysis; the mechanism of the reaction is considered to go as
follows in homogenous state [5,6]:
* Corresponding author. Tel.: +86 351 4049612; fax: +86 351 4041153.
E-mail address: yhsun@sxicc.ac.cn (Y. Sun).
The epoxide ring of propylene oxide may open at either
of the CO bonds. In basic catalysis, the bond preferentially
opens at the least sterically hindered position, leading to
mostly secondary alcohols. But acid catalysts provide a
mixture of secondary and primary alcohols, the proportion
of which depends on the acid strength, and the primary
alcohol was revealed the reproduction and developmental
toxicity [7]. Therefore, the high selectivity is required for
this process.
The catalysts used earlier were homogenous bases or
acids (NaOH, alcoholic sodium and BF3). Homogenous base
catalysts showed the high activity or selectivity, but they
suffer from the drawbacks of separation, liquid waste
treatment and corrosion problems. Solid acid catalysts, such
as acid zeolites [8] and cation-exchangeable layered clay

0926-860X/$ see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2005.07.005
 W. Zhang et al. / Applied Catalysis A: General 294 (2005) 188196
[9], had good activity but lower selectivity to 1-alkoxy-2-
propanol.
Solid basic catalysts, including anionic double hydroxide
clays [10], magnesiumaluminum oxide [11] and basic
zeolites [12], have attracted much attention due to their high
selectivity of 1-alkoxy-2-propanol. Unfortunately, few
studies have reported the reaction mechanism on the
methanol addition to propylene oxide over solid base
catalysts. There are many differences between homogenous
reactions and heterogeneous ones. First, a heterogeneous
reaction proceeds on the surface of solid catalyst, and only
those propylene oxides that are close to the surface have the
chance to take part in the reaction. Second, the hetero-
geneous basic catalysis is more complex than the homo-
genous type in most circumstances. Thus, it is possible that a
different reaction mechanism may exist over solid base
catalysis. The present work focused on the understanding of
propylene glycol ether synthesis from methanol and
propylene oxide over solid bases. Considering the high
performance of alkaline earth metal oxides in a variety of
organic reactions involving formation of carbanion inter-
mediates [1317], we chose MgO as model catalysts, and
both CaO and Al2O3 were studied for comparison as well.
2. Experimental
2.1. Catalyst preparation
MgO was obtained by thermal decomposition of
Mg(OH)2 at 673, 773, 873, and 973 K, respectively. CaO
was prepared from CaCO3 calcined at 1073 K in N2
atmosphere, and Al2O3 was supplied by Tianjin Fuchen
Chemical industries (SBET = 128 m2/g). BET surface areas
of the samples were determined by the BET method through
micromeritics ASAP-2000.
2.2. Temperature programmed desorption of CO2 and
methanol
Each catalyst sample (0.1 g, 4060 mesh) was placed in the
quartz reactor and was pre-treated in Ar for 1 h at the desired
temperature, and then was cooled to room temperature, CO2
was quantitatively adsorbed by each sample in a pulse valve.
TPD was carried out with a heating rate of 10 K/min under Ar
flow of 50 ml/min, and the effluent was detected by a
BALZAQ-mass spectrometer. For CH3OH-TPD, the catalyst
pre-treatment was carried out as CO2-TPD. Methanol was
injected by using a 1 ml syringe at room temperature, and after
it was purged off in Ar, the TPD of adsorbed methanol started
with the same procedure as that used for CO2-TPD.
2.3. Propylene oxide pulse reaction
Each catalyst was pre-treated in the same way as in the
TPD procedure. Propylene oxide was injected with a 1 ml
189
syringe at 323 K, and the effluents were detected by a
BALZQ-mass spectrometer.
2.4. FT-IR of adsorbed methanol and propylene oxide
FT-IR spectra were recorded on a Nicolet Magna 550II
Fourier-transform infrared spectrometer in the region 4000
1000 cm 1; 128 scans with a resolution of 4 cm 1 were
collected. A magnesium oxide disc, pressed at 2.4 
108 Nm 2 and weighing 1520 mg, was thermally pre-
treated by heating at 673 K in vacuo. The build-up of
methanol and propylene oxide species on the surface was
performed by adding their vapors, which had been degassed
by freezing and pumping several times, to the cell for 15 min
(propylene oxide for 10 s) at a desired temperature. After was
removed by evacuation, FT-IR spectra of surface species were
obtained.
2.5. Catalytic performance
The reaction was carried out in a 75 ml batch reactor, with
the mole ratio of methanol and propylene oxide being 5:1.
After running at 393 K for 5 h under magnetic stirring, the
reactor was cooled down to room temperature. The products
were analyzed by a gas chromatograph with a flame ionization
detector after centrifugal separation from the catalyst.
3. Results
3.1. Basic properties and catalytic performance
Fig. 1 depicts the TPD profiles of CO2 adsorbed on MgO,
CaO and Al2O3. For MgO and Al2O3, a CO2 desorption peak
was observed around 373 K. In a higher temperature region
above 473 K, two peaks were observed at 503 and 573 K for
MgO, and a trace amount of CO2 desorption was observed
above 473 K on Al2O3. On the other hand, a large amount of
CO2 evolution centered at 923 K took place on CaO. This
strongly suggested that a few weak basic sites were present
on Al2O3, while a large amount of moderate basic sites were
present on MgO and strong basic sites were present on CaO.
The addition reaction of propylene oxide with methanol
strongly depended on catalyst (see Fig. 2). MgO was found
to be more active and selective than CaO for the formation of
1-methoxy-2-propanol. Al2O3 showed high propylene oxide
conversion (98.2%), but low selectivity toward 1-methoxy-
2-propanol. These results indicated that an appropriate base
strength was required for high selectivity to 1-methoxy-2-
propanol. It seemed that the formation of 1-methoxy-2-
propanol was closely related to the base strength.
Fig. 3 shows the catalytic performance of MgO calcined
at various temperatures. The activity decreased with the rise
of calcination temperature, but the selectivity to 1-methoxy-
2-propanol varied only a little. The BET surface area and
CO2 uptake listed in Table 1 illustrate both BET surface area
190 W. Zhang et al. / Applied Catalysis A: General 294 (2005) 188196
Fig. 1. CO2-TPD of MgO, CaO and Al2O3.
and CO2 uptake at the moderate basic sites decreased
with the rise of calcination temperature. As a result, the
conversion of propylene oxide and the CO2 uptake at
moderate basic site could be lineally correlated, as shown in
Fig. 4, i.e. the basic sites with moderate strength appeared to
be the active sites for the formation of 1-methoxy-2-
propanol. The lower selectivity to 1-methoxy-2-propanol of
Al2O3 would be ascribed to its acidity (not shown here).
3.2. Methanol adsorption and desorption on MgO
The adsorption of methanol on MgO at various
temperatures was investigated by FT-IR (see Fig. 5). An
intense band at 1450 cm 1 was observed over MgO pre-
treated at 673 K in vacuum; this band could be assigned to
the MgCO3 stretching vibration. When methanol was
adsorbed onto the MgO surface, the bands were observed
at 2915, 2861, and 2800 cm 1 and at 1097 and 1055 cm 1,
corresponding to the CH and the CO stretching vibrations
Fig. 2. Comparison of catalytic properties of MgO, CaO and Al2O3.
due to the formation of methoxide species. Tench et al. [18]
reported that the introduction of methanol onto MgO led to
the appearance of two strong bands at 1114 and 1060 cm 1,
the latter being largely removed by pumping at RT. They were
assigned to an undissociated methanol species and a meth-
oxide species, respectively. Our results were similar with their
work, but the band at 1055 cm 1 could not be removed by
pumping at RT or even at 323 K. As the temperature was
increased from RT to 423 K, the band intensity at 2800 and
1097 cm 1 (1106 cm 1 323 K) increased while it decreased
at 1055 cm 1. This was reasonable if the bands at 1106 and
1055 cm 1 were due to two kinds of methoxide species. The
new OH group that formed from the dissociative adsorption
gave rise to broad bands near 3600 cm 1. When the
adsorption temperature reached 393 K, new bands appeared
at 1599 and 1394 cm 1, these could be ascribed to the
transformation of methoxide species into formate ions
[19,20]. However, for methanol adsorbed on CaO (see
Fig. 6), the bands around 2800 cm 1 and 12001000 cm 1
Fig. 3. The effect of calcination temperature on MgO activity.
 W. Zhang et al. / Applied Catalysis A: General 294 (2005) 188196 191

Table 1
BET surface area and CO2 uptake of MgO calcined at various temperatures
Calcination temperature (K) BET surface area (m2/g) CO2 uptake (mmol/g)
373 K 503 and 573 K 923 K
4 2
673 198.73 6.20  10 2.58  10
4 2
773 150.49 8.31  10 1.89  10
3 2 4
873 105.92 1.63  10 1.24  10 6.26  10
3 2 4
973 96.92 2.11  10 1.18  10 6.99  10

Fig. 4. The relationship between activity and MgO basicity.

Fig. 6. IR spectra of methanol adsorbed On CaO at various temperatures:
(1, RT; 2, 383 K; 3, 473 K).

were not clearly observed, and only trace adsorption took
place. At the same time, the broad bands due to hydroxyl
groups were not easily observed near 3600 cm 1.
The TPD of methanol over MgO indicated that methanol
desorbed with the maximum at 432 K (see Fig. 7), and CO2
and CO desorption peaks were observed at the high
temperature region. Thus, methanol adsorbed onto MgO in
both undissociated and dissociated forms, in agreement with
the FT-IR results. Undissociated methanol could be removed
by pumping at RT and was not observed by FT-IR, because it
coordinated to the catalyst surface in a weakly absorbed
molecular state, corresponding to the methanol desorption at
low temperature. Dissociated methanol produced methoxide
species and desorbed into CO2 and CO at high temperature.

Fig. 7. TPD of adsorbed methanol on MgO: (m/e = 31, 28 and 44 corre-

Fig. 5. IR spectra of methanol adsorbed on MgO at various temperatures: sponding to the strongest mass spectra signal of methanol, CO and CO2,
(1, MgO; 2, RT; 3, 323 K; 4, 363 K; 5, 393 K; 6, 423 K). respectively.).
192 W. Zhang et al. / Applied Catalysis A: General 294 (2005) 188196

Fig. 9. FT-IR spectra of PO absorbed on MgO at various temperature: (1,

Fig. 8. TPD of adsorbed methanol on CaO. MgO; 2, RT; 3, 323 K; 4, 363 K; 5, 393 K; 6, liquid PO).

However, only methanol desorption was observed with the increased simultaneously with the rise of adsorption
maximum in TPD patterns at 609 K on CaO (see Fig. 8). temperature (see Fig. 9 line 25), suggesting that the epoxide
Unlike MgO, CO2 and CO were not observed in the high ring opened and formed propylene-like species. In addition,
temperature region, and these results suggested that no the bands at 2964, 2852, 2782 and 2653 cm 1 were assigned
methanol dissociation took place on CaO (trace dissociation to CH asymmetrical and symmetrical vibrations of the methyl
might be possible). Although CaO had the strong basic group. The bands around 3600 cm 1 were characteristic of
strength and high basicity, methanol was hard to dissociate to stretching vibrations of the hydroxyl group in the various
form methoxide species on CaO surface. Because of the environments. The increase of those broad bands with the rise
strong basic strength of the oxygen anion, methanol in of adsorption temperature suggested that the proton abstrac-
molecular state would be coordinated to the CaO surface in a tion from propylene oxide took place in the process of
stronger manner than that of MgO, leading to the desorption at formation of propylene-like species.
higher temperature. Fig. 10 shows the stability of the propylene-like specie on
MgO. In order to quantify the stability of propylene-like
3.3. Adsorption and desorption of propylene species, we analyzed the area of band at 3080 cm 1 evacuated
oxide on MgO at various temperatures using curve-resolving techniques
with a Gaussian method. The band area varied a little untill
The rapid adsorption of propylene oxide vapor (Pe = the evacuation temperature reached 393 K. Afterwards, the
10 Torr) at various temperatures was investigated by FT-IR band area decreased drastically, and when the evacuation
(see Fig. 9). Compared with the spectrum of pre-treated
MgO (Fig. 9, line 1), four groups of bands were clearly
visible in the regions near 3600, 30802653, 1644 and
1164 cm 1. However, the characteristic bands of propylene
oxide at 3050 cm 1 (CH stretching in epoxide ring) and
1260 cm 1 (epoxide ring breathing) were not observed
when 10 Torr propylene oxide vapor was introduced at room
temperature (see Fig. 9 line 2). The band at 1164 cm 1 could
be associated with the CO stretching vibration. The epoxide
ring probably opened and the CO bond was formed by the
interaction of propylene oxide with the MgO surface, and
then the intensity grew with the rise of adsorption
temperature (see Fig. 9 line 25).
In the CH stretching region, bands appeared at 3080, 2964,
2852, 2782 and 2653 cm 1. Therein, the band at 3080 cm 1
should be most interesting. As is well known, alkenes species
showed the CH stretching vibration at high wave numbers.
Furthermore, the characteristic stretching band of C C at Fig. 10. The stability of absorbed species on MgO with the rising evacua-
1644 cm 1 was also observed in our work. These two bands tion temperature.
 W. Zhang et al. / Applied Catalysis A: General 294 (2005) 188196 193

Fig. 11. PO pulse reaction over MgO at 323 K: (m/e = 28 and, 43 corre-
sponding to the strongest mass spectra signal of propylene oxide and Fig. 12. IR spectra of MeOH and PO co-adsorption on MgO: (1, MgO; 2,
acetone, respectively). MeOH adsorbed on MgO at RT; 3, PO introduced at RT; 4, PO introduced at
373 K).

temperature reached 453 K, only a little propylene-like room temperature, the bands at 3080 and 1644 cm 1 were
species were present on the surface. These illustrated that the clearly observed (see Fig. 13 line 1). However, with the
propylene-like species were stable to some extent, although introduction of methanol, no clear presence of propylene-
they would be desorbed or decomposed at higher temperature. like specie could be detected, because the bands at 3080 and
Fig. 11 shows the results of propylene oxide pulse 1644 cm 1 were hardly visible (see Fig. 13 line 2). At the
reaction. As soon as the propylene oxide was injected to the same time, the band at 1097 cm 1 was strong and sharp,
pulse reactor in which MgO was loaded, propylene oxide (m/ which indicated the formation of 1-methoxy-2-propanol, as
e = 28) and acetone (m/e = 43) were detected. Molnar et al. mentioned above. The bands at 1106 and 1055 cm 1, which
[21] have also found the same results. Compared with the correspond to the methoxide formation, were not observed
FT-IR results, the propylene-like species are similar to in this process. When methanol was introduced at 373 K, the
enolate that readily changes to acetone. band at 1097 cm 1 became stronger and sharper (see Fig. 13
line 3). Thus, the propylene-like species were involved in the
3.4. Co-adsorption of methanol and propylene formation of 1-methoxy-2-propanol in this experiment.
oxide on MgO At last, propylene oxide and methanol were introduced at
the same time (see Fig. 14). Once the propylene oxide and
In order to understand the interaction between the methanol were introduced at room temperature, the weak
methoxide and propylene-like species on MgO, we carried
out two co-adsorption experiments with the different intro-
ductions of methanol and propylene oxide. In the first
experiment, methanol was introduced first onto activated
MgO pellets, followed by propylene oxide, and then the
system was evacuated at room temperature (see Fig. 12).
Obviously, the intensity of the bands at 1106 and 1055 cm 1,
which were the symbol of methoxide, was weakened when the
propylene oxide was introduced at room temperature (see
Fig. 12 line 3). However, the adsorption of propylene oxide on
MgO, which led to the particular bands at 3080 and
1644 cm 1 (see Fig. 9), was not observed in this process.
It was interesting that if the propylene oxide was introduced
at 373 K as shown in line 4, the band at 1055 cm 1 disappea-
red and the spectrum presented a new band at 1097 cm 1,
which might be assigned to CO stretching vibration of 1-
methoxy-2-propanol. This suggested that methoxide takes
part in the formation of 1-methoxy-2-propanol. Fig. 13. IR spectra of PO and MeOH co-adsorption on MgO: (1, PO
The reverse process was carried out in the second adsorbed on MgO at RT; 2, MeOH introduced at RT; 3, MeOH introduced
experiment. Once the propylene oxide was introduced at at 373 K).
194 W. Zhang et al. / Applied Catalysis A: General 294 (2005) 188196
Fig. 14. IR spectra of MeOH and PO introduced at the same time on MgO:
(1, MgO; 2, MEOH and PO introduced at 298 K; 3, MEOH and PO
introdued at 373 K).
band at 1644 cm 1 was observed, and the band at 1055 cm 1
that is assigned to methoxy group was also observed. With
the adsorption temperature rise to 373 K, the band at
1097 cm 1 was clear and strong and the bands at 1644 and
1055 cm 1 disappeared.
The co-adsorption results described above clearly
illustrate that methanol and propylene oxide were activated
on the MgO surface and then both methoxide and propylene-
like species appeared that interacted with each other to form
1-methoxy-2-propanol.
4. Discussion
4.1. Effect of acidbase properties on the synthesis of
1-methoxy-2-propanol
Compared with CaO and Al2O3, MgO with moderate
basicity showed high PO conversion and isomer selectivity
(see Fig. 2). Although CaO had strong basicity, it had low
Scheme 1. Proposed formation mechanism of propylene-like species on MgO.
activity. This indicated that the synthesis of 1-methoxy-2-
propanol should be closely related to the basic sites with
moderate strength. Furthermore, MgO pre-treated at
various temperatures, which led to the different amount
of moderate base sites, showed an interesting relationship
between basicity and catalytic performance, i.e. the PO
conversion could be lineally correlated with the amount of
moderate basicity (see Fig. 4). Thus, the base sites with
moderate strength favored the formation of 1-methoxy-2-
propanol. Such an observation could be related with the
acidbase properties of MgO [22]. As mentioned above,
FT-IR illustrated that methanol absorbed on MgO could
generate undissociated methanol and then dissociated
species. The latter produced methoxide species and reacted
with propylene oxide to form 1-methoxy-2-propanol. As
far as CaO was concerned, no methoxide species were
formed on the surface, because the acid strength of Can+
cation was too weak to stabilize the methoxide species, and
then CaO showed low catalytic activity. Thus, the
formation of methoxide species was very important for
the synthesis of 1-methoxy-2-propanol. The basic sites
were needed for methanol dehydrogenation, whereas the
acidic sites were needed to stabilize the methoxide. In the
case of Al2O3, the acid sites were predominant on the
surface [23], which resulted in low selectivity to 1-
methoxy-2-propanol, where Al2O3 could cause the reaction
in an acid catalyzed route due to its acidity, being indicative
of the isomer production.
4.2. Mechanism of formation of propylene-like specie
Propylene oxide could be adsorbed molecularly with the
oxygen atom bound to the MgO surface and the epoxide
ring perpendicular to the surface plane as proposed by
Dinger et al. for propylene oxide adsorbed on Pt (1 1 0)
[24]. In the present work, the acid site (magnesium ion)
coordinated with the oxygen atom in the epoxide ring. As a
result of the electron withdrawal induced by the positive
charge developing on the oxygen in the transition state, the
bond between the oxygen and the primary carbon atom C
(3) underwent cleavage (the electrons on C (2) could be
 W. Zhang et al. / Applied Catalysis A: General 294 (2005) 188196
Scheme 2. Plausible mechanism of 1-methoxy-2-propanol formation.
partly compensated by the electron donation of methyl
group). Such a ring opening led to the formation of the
more stable carbanion. The proposed reaction steps took
place as follows (see Scheme 1): the propylene oxide was
adsorbed on the active centers, and oxygen in the epoxide
ring interacted with the surface cation (Mgn+). As a result,
a carbanion was formed by OC (3) bond breaking induced
by Mgn+ in the second step, and then the rearrangement
reaction took place via the abstraction of proton with basic
site (oxygen anion), where the propylene-like speices was
formed.
4.3. Mechanism of formation of 1-methoxy-2-propanol
on MgO
Methanol and propylene oxide adsorbed on MgO
combined to form methoxide and propylene-like species.
The addition of methanol to alkenes species might occur in a
Markownikov fashion and resulted in the formation of 2-
methoxy-1-propanol. However, such an addition mainly
yielded 1-methoxy-2-propanol over MgO in the present
work (see Fig. 2). Apparently, the addition of methanol
followed an anti-Markownikov fashion. One plausible
mechanism could be illustrated in Scheme 2. A proton
was abstracted from methanol to form a methoxide ion, and
then adsorbed on the MgO surface. At the same time,
propylene-like species were formed by the adsorption of
propylene oxide as described in Scheme 1. Afterwards, the
addition of methoxide to propylene-like species took place
in an anti-Markownikov fashion and produced 1-methoxy-2-
propanol anion, followed by capturing a surface proton to
form 1-methoxy-2-propanol, which was adsorbed on surface
or desorbed into gas phase. In this process, the presence of
the methyl substitution on C (2) gave rise to steric hindrance
against attack on this carbon, and a difference in polarization
between C (2) and C (3) induced by the electron-releasing
methyl group might also contribute to the favored attack on
195
C (3). Thus, the addition reaction took place in anti-
Markownikov fashion.
A similar anionic mechanism was proposed in cya-
noethylation of alcohol to 3-alkoxypropanenitrile [25] and
addition of methanol to allyl alcohol [26]. It seemed
reasonable if high activity and selectivity were due to the
ability of both methoxide ion generation and propylene
oxide activation on MgO. The types of basic sites on the
MgO surface included surface hydroxyl group, Lewis-acid
Bronsted-base pairs (Mgn+O2 pair site) and isolated
surface O2 ions [27,28]. The basic strength of surface
hydroxyls was considered to be very low [27], which might
correspond to the desorption peak at 373 K (see Fig. 1). This
type of basic sites might be not strong enough to dissociate
methanol and abstract a proton from propylene oxide. The
moderate basic sites of Lewis-acidBronsted-base pairs and
isolated surface O2 ions were appropriate to dissociate
methanol to methoxide and had the ability to abstract a
proton from propylene oxide. CaO with only strong basic
sites seemed unfavorable because of strong adsorption of
methanol (see Fig. 8). Thus, moderate basic sites should be
the active sites for the present reaction.
5. Conclusion
MgO was an efficient catalyst for the synthesis of 1-
methoxy-2-propanol from methanol and propylene oxide.
Such a reaction required appropriate base strength to obtain
high activity and selectivity. The basic sites with moderate
strength were predominant on MgO surface, i.e. oxygen in
MgO pairs and isolated O2 anions, and they preferentially
catalyzed the reaction by liable formation of methoxide and
carbanion intermediates. The addition of methoxide to
propylene-like species took place in anti-Markownikov
fashion and then selectively produced 1-methoxy-2-
propanol.
196 W. Zhang et al. / Applied Catalysis A: General 294 (2005) 188196
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