Oligomerization of α-methylstyrene in the presence of mordenite type zeolite

Article abstract of DOI:10.1023/A:1022282408117

The activity and selectivity of coarse-porous H-mordenite in synthesis of cyclic and linear dimers of α-methylstyrene were studied.

Full text of DOI:10.1023/A:1022282408117

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Russian Journal of Applied Chemistry, Vol. 75, No. 9, 2002, pp. 1539 1540. Translated from Zhurnal Prikladnoi Khimii, Vol. 75, No. 9,
2002, pp. 1574 1575.
Original Russian Text Copyright
2002 by Grigor’eva, Kutepov, Makhamatkhanov, Bikbaev, Khazipova, Kovtunenko.
BRIEF
COMMUNICATIONS
Oligomerization of -Methylstyrene in the Presence
of Mordenite Type Zeolite
N. G. Grigor’eva, B. I. Kutepov, R. A. Makhamatkhanov, R. T. Bikbaev,
A. N. Khazipova, and I. A. Kovtunenko
Institute of Petrochemistry and Catalysis, Bashkortostan Academy of Sciences and Ufa Scientific Center,
Russian Academy of Sciences, Ufa, Bashkortostan, Russia
Received October 15, 2001; in final form, January 2002
Abstract The activity and selectivity of coarse-porous H-mordenite in synthesis of cyclic and linear dimers
of -methylstyrene were studied.
Numerous homogeneous and heterogeneous acid
catalysts are used to synthesize dimers and trimers of
-methylstyrene; these include sulfuric, phosphoric,
chloroacetic, and p-toluenesulfonic acids, cation-
exchange resins [1, 2], metal oxides [3], and zeolite-
like aluminophosphates [4]. However, data on the
effect of zeolites in this reaction are scarce. Synthesis
of linear dimers of -methylstyrene in CH Cl
solution in the presence of zeolites Y with various
Brønsted acidities was studied in [5]. Utilization of a
solvent in this case requires additional stage of distil-
lation, which complicates the process and deteriorates
its feasibility characteristics.
were treated with NH NO solutions to the residual
4 3
content of Na O 0.1 wt % and then calcined in air
2
for 4 h at 540 C.
As in the case of the other acid catalysts [1 5],
oligomerization of -methylstyrene on mordenite
yields the cyclic dimer c-D (1,1,3-trimethyl-3-phenyl-
indane), linear dimers -D and -D (4-methyl-2,4-di-
phenyl-1-pentene and 4-methyl-2,4-diphenyl-2-pen-
tene), trimers, and tetramers. The composition of the
reaction products is determined by the catalyst prop-
erties and reaction conditions.
2
2
As seen from Table 1, Na-mordenite is inactive in
this reaction, whereas the H-form exhibits a catalytic
activity strongly depending on the pore size in the
mordenite crystal lattice. No conversion of -methyl-
styrene occurs at 120 140 C in 6 h with fine-porous
mordenite I (10 20 wt % relative to the feed), and
significant conversion K is observed only in the pres-
ence of 50 60 wt % of this catalyst, which suggests
that the reaction proceeds predominantly at the outer
zeolite surface.
In this work we studied oligomerization of -meth-
ylstyrene in the presence of mordenite type zeolite.
EXPERIMENTAL
Oligomerization of -methylstyrene was performed
in a batch reactor at atmospheric pressure in the 20
140 C range. The reaction products were analyzed by
gas liquid chromatography (GLC).
The mordenite type zeolites were prepared from
aqueous solutions of sodium aluminate, sodium hy-
droxide, and white black (samples I, II) or the waste
from production of crystalline silicon (sample III)
[6, 7]. The SiO /Al O molar ratio in the resulting
In the presence of coarse-porous catalysts II and III,
a mixture of -methylstyrene oligomers is formed,
and in the case of catalyst III the content of trimers
and tetramers reaches 30 wt %.
2
2 3
Mordenite II is the most active and selective cata-
lyst providing conversion of -methylstyrene into the
linear dimers -D and -D. The data on oligomeriza-
tion of -methylstyrene in the presence of this catalyst
at various temperatures are listed in Table 2. The reac-
tion starts even at a low content of catalyst II (1
2 wt %) at 60 C, with the selectivity S of formation
of dimers -D and -D being 61.4%; however, the
samples was 12.2 (I), 9.8 (II), and 10.0 (III). Sam-
ple I was a fine-porous (static capacity for benzene
3
1
vapor 0.02 cm g ), and samples II and III, coarse-
porous (static capacity for benzene vapor 0.11 and
3
1
0.12 cm g , respectively) modifications of morde-
nite.
To prepare catalysts in the H form, the samples
1070-4272/02/7509-1539$27.00 2002 MAIK Nauka/Interperiodica

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1540
GRIGOR’EVA et al.
Table 1. Oligomerization of -methylstyrene in the presence of mordenite type zeolite
Composition, wt %
ccat
,
Catalyst
T,
C
, h
K, %
wt %
c-D
-D
-D
trimers
Na-II
I
1
20
10
20
50
10
10
20
120
10
8
6
6
4
0.5
6
0
0
0
0
82.2
83.5
62.0
94.0
100
120
140
120
100
100
120
1.8
3.4
2.1
64.0
73.1
41.3
31.2
0.4
1.1
0.5
16.0
5.9
18.1
25.8
II
III
7
17.3
19.7
Table 2. Dimerization of -methylstyrene in the presence of mordenite II
Composition, wt %
c
cat, wt %
T,
C
, h
K, %
S, %
c-D
-D
-D
trimers
1
2
5
120
6
5
3
1
2.0
4.7
2.8
2.0
3.2
3.3
3.7
9.8
14.6
4.9
10.0
8.5
0.2
0.1
4.0
1.3
2.1
0.8
2.2
2.0
15.8
0.6
12.2
14.0
78.6
74.0
87.4
74.8
83.8
81.5
96.8
91.8
97.3
100.0
83.6
61.4
78.2
90.4
83.4
87.8
88.3
78.2
71.2
85.8
78.0
60
100
80
0.7
14.3
5.1
11.3
5.8
6.1
8.0
12.7
8.1
11.2
6.7
57.5
65.6
70.8
64.9
71.8
61.7
52.7
78.2
59.6
10
2
10
10
100
110
0.25
1.0
0.25
2.0
1
15
20
20
100
100
140
1
1
10.2
93.3
16.3
monomer conversion is relatively low. With increas-
ing content of the catalyst to 10 15 wt %, at 80
110 C, the conversion of -methylstyrene reaches
97%, with 80 90% selectivity. Under the more rigid
conditions, the yield of the cyclic dimer increases, and
at 140 C and 20 wt % content of mordenite II the
yield of c-D is 93.3 wt %.
droxide, and white black with the subsequent removal
of cations and annealing at 540 C exhibits high activ-
ity and selectivity in oligomerization of -methyl-
styrene.
REFERENCES
1. The Chemistry of Cationic Polymerization, Plesch, P.H.,
It should be noted that mordenites II and III, hav-
ing similar characteristics, differ in the catalytic prop-
erties: The conversion of -methylstyrene and selec-
tivity in the presence of catalyst II are significantly
higher as compared to catalyst III. This is probably
due to the different composition of the initial silicon-
containing materials used in the mordenite prepara-
tion.
Ed., Oxford: Pergamon, 1963.
2. Chaudhuri, B. and Sharma, M.M., Ind. Eng. Chem.
Res., 1989, no. 28, pp. 1757 1763.
3. Kawakami, Y., Toyshima, N., Ando, T., and Yamashi-
ta, Y., Polym. J., 1981, vol. 13, no. 10, pp. 947 953.
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Prikl. Khim., 2000, vol. 73, no. 5, pp. 787 790.
CONCLUSION
6. RF Patent 2160228.
7. Pavlov, M.L., Makhamatkhanov, R.A., Kutepov, B.I.,
et al., Zh. Prikl. Khim., 2001, vol. 74, no. 2, pp. 328
330.
The coarse-porous H-mordenite prepared from the
aqueous solutions of sodium aluminate, sodium hy-
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 75 No. 9 2002