Selective Catalytic Hydrogenation of Alicyclic Dienes with Hydrogen in a Liquid Phase

Article abstract of DOI:10.1134/S0965544118100031

Abstract: The hydrogenation behavior of a number of alicyclic dienes (5-vinyl-2-norbornene (5-vinyl-bicyclo[2.2.1]heptene-2), dicyclopentadiene (tricyclo[5.2.1.0^2,6]decadiene-3,8), and cis,cis-1,5-cyclooctadiene) to the corresponding cycloalkenes in the presence of a finely divided palladium catalyst suspended in the liquid phase has been studied. The reactivities of the double bonds of these dienes have been compared. The conversion of 5-vinyl-2-norbornene and selectivity of its hydrogenation to 2-vinylnorbornane depending on the reaction conditions have been evaluated. Conditions for the selective production of desired 2-vinylnorbornane are proposed for the further implementation of this process in practice.

Full text of DOI:10.1134/S0965544118100031

ISSN 0965-5441, Petroleum Chemistry, 2018, Vol. 58, No. 10, pp. 869–875. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © M.V. Bermeshev, T.N. Antonova, D.R. Shangareev, A.S. Danilova, N.A. Pozharskaya, 2018, published in Neftekhimiya, 2018, Vol. 58, No. 5, pp. 580–587.
Selective Catalytic Hydrogenation of Alicyclic Dienes
with Hydrogen in a Liquid Phase
M. V. Bermesheva, b, *, T. N. Antonovac, **, D. R. Shangareevc, A. S. Danilovac, and N. A. Pozharskayab
aTopchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 119991 Russia
bMendeleyev University of Chemical Technology of Russia, Moscow, 125047 Russia
cYaroslavl State Technical University, Yaroslavl, 150023 Russia
*e-mail: bmv@ips.ac.ru
**e-mail: antonovatn@ystu.ru
Received March 13, 2018
Abstract—The hydrogenation behavior of a number of alicyclic dienes (5-vinyl-2-norbornene (5-vinyl-bicy-
clo[2.2.1]heptene-2), dicyclopentadiene (tricyclo[5.2.1.02,6]decadiene-3,8), and cis,cis-1,5-cyclooctadiene)
to the corresponding cycloalkenes in the presence of a finely divided palladium catalyst suspended in the liq-
uid phase has been studied. The reactivities of the double bonds of these dienes have been compared. The
conversion of 5-vinyl-2-norbornene and selectivity of its hydrogenation to 2-vinylnorbornane depending on
the reaction conditions have been evaluated. Conditions for the selective production of desired 2-vinylnor-
bornane are proposed for the further implementation of this process in practice.
Keywords: 5-vinyl-2-norbornene, 2-vinylnorbornane, dicyclopentadiene, 1,5-cyclooctadiene, liquid-phase
hydrogenation, finely divided catalysts, double bond reactivity
DOI: 10.1134/S0965544118100031
The hydrogenation of one of the double bonds in ing the corresponding cyclodienes. In addition, its use
alicyclic dienes to form corresponding cycloalkenes is under the conditions of vigorous stirring converts the
of interest for further synthesis of derivatives with dif- three-phase gas/liquid/solid-catalyst system to the
ferent functionalities, polymers for the fabrication of state of pseudohomogeneity, in which the reaction can
molded articles, and other materials with a set of valu- be kinetically controlled mode and, hence, modeling
able performance characteristics on their basis [1, 2]. of this process is possible [6].
The efficiency of the application of cycloalkenes for
practical purposes largely depends on the selectivity of
their formation in the hydrogenation process, which
can take place only in the case of successive saturation
of the double bonds of cyclodienes.
In this paper, we present the results of studying the
basic features of hydrogenation of 5-vinyl-2-nor-
bornene (VNB) to 2-vinylnorbornane using a finely
divided catalyst (1% Pd/C) suspended in the liquid
phase in comparison with the similar results of the sat-
uration of double bonds of alicyclic dienes, such as
dicyclopentadiene and 1,5-cyclooctadiene.
The liquid-phase hydrogenation of VNB with
hydrogen has been investigated earlier but mainly with
the use of molded catalysts of the platinum group [7–
9]. According to the data presented in [7], in the pres-
ence of silica gel-supported catalysts, such as Ru, Rh,
Ir, and their mixtures, the endo- and exo-isomers of
VNB taken at a 2 : 1 ratio are nonselectively hydroge-
nated at the double bond of the bicycloheptene moiety
of the molecule and its vinyl group simultaneously.
For this reason, endo-5-ethylnorbornene and endo-2-
vinylnorbornane, as well as their exo-isomers,
are simultaneously formed as the main reaction prod-
ucts. According to Kohlman et al. [8], a high yield of
2-vinylnorbornane is achieved in the case of using
0.5% Pd/γ-Al2O3 with a 15% CaO additive as the cat-
This catalyst is distinguished by high activity due to
its structure, in which “amorphous carbon–Pd” thin
composite layers provide the nanoscale dimensional-
ity of the metal particles (20–900 nm) and allow car- alyst if the VNB hydrogenation process is performed
rying out the hydrogenation reaction at atmospheric under a hydrogen pressure of up to 10 atm in methanol
pressure, moderate temperatures, and without prelim- as the solvent in the presence of poisoning additives
inary activation according to published data [3]. As is (gaseous CO or pyridine). The introduction of poi-
shown in [4, 5], the application of a finely divided cat- soning additives undoubtedly decreases the techno-
alyst provides the selective formation of a number of logical effectiveness and environmental safety of such
cycloalkenes at a level of 92–98 mol % by hydrogenat- a process in the case of its practical implementation. It
869

870
BERMESHEV et al.
Table 1. Rate ratios in the successive hydrogenation of double bonds of alicyclic dienes depending on their structure. The
catalyst (1% Pd/C) concentration is 4 g/dm3
Cyclodiene hydrogenation
Cycloalkene hydrogenation
Weff1
Weff2
Alicyclic
diene
rate (Weff1),
mol 9dm−3 min−10
rate (Weff2),
mol 9dm−3 min−10
Solvent
T, K
VNB
Pseudocumene*
Toluene
323
333
333
333
343
343
0.0411
0.0210
0.0343
0.0188
0.0350
0.0092
0.0080
0.0142
0.0028
0.0031
0.0053
4.47
2.63
2.42
6.71
11.2
DCPD
COD**
Cyclooctane
Toluene
Toluene
_
0.0536
10.1
3
* The activating additive is ionol; ** the catalyst concentration is 6 g/dm .
was also noted [9] that in the case of hydrogenation of finding that is in contradiction with the data of the
patent [8].
VNB in a cyclohexane solution in the presence of bar-
ium sulfate-supported palladium for 6 h at 80°C and a
hydrogen pressure of 2 atm, the yield of 2-vinylnor-
bornane of about 92% is provided with the complete
conversion of the reactant diolefin. However, when
methanol is used as the solvent, the selectivity for 2-
vinylnorbornane sharply decreases and does not
Since 5-vinyl-2-norbornene (5-vinyl-bicyclo [2, 2,
1]heptene-2) (VNB), dicyclopentadiene (tricy-
clo[5.2.1.02,6]decadiene-3,8) (DCPD), and cis,cis-
cyclooctadiene-1,5 (COD) are cyclodienes that differ
in structure, a comparative investigation of the process
of their liquid-phase hydrogenation with hydrogen
exceed 40% despite the full conversion of VNB, a with regard to double bond reactivity in the case of
(a) (b)
4
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
1 2
3
0
60
120
180
240
Time, min
3
Fig. 1. (a) Rate curve of hydrogen uptake in the VNB of hydrogenation process. The solvent is toluene, C
= 2.2 mol/dm ,
0, VNB
3
C
= 4 g/dm , and the temperature is 333 K. (b) Chromatogram of the products of hydrogenation of COD at its conversion of
cat
20%: (1) cyclooctene, (2, 3) intermediate products, and (4) COD.
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SELECTIVE CATALYTIC HYDROGENATION OF ALICYCLIC DIENES
871
using 1% Pd/C slurry is not only of practical, but also It is known from published data [10] that these hydro-
of scientific interest.
carbons are capable of differentiating the rates of
hydrogenation of the double bonds of alicyclic dienes
in the case of their successive saturation.
EXPERIMENTAL
The successive character of the VNB process
hydrogenation is evidenced by the results presented in
Fig. 1a, showing that the rate curve of hydrogen
uptake in the process under study has two rectilinear
portions, which allow estimating the value of the
hydrogen absorption rate at the first and the second
step and then the ratio of the obtained values as well
(Table 1). It is seen from the data of Table 1 that the
ratio of the hydrogen uptake rates at the two steps is
primarily determined by the structure of the alicyclic
diene being hydrogenated.
The hydrogenation of cyclodienes was performed
in a three-phase gas/liquid/solid-catalyst system in
both a batch volumetric unit and a continuous-flow
system in a thermostated reactor which modeled a per-
fectly mixed reactor and was equipped with a stirrer, a
hydrogen feed diffuser, a reflux condenser with an
entrainment separator, and a thermometer.
The experiments were assessed by the amount of
absorbed hydrogen and concentration of the reaction
products in the reaction mixture which were analyzed
via gas–liquid chromatography on a Chromatec
Kristall 5000.2 (Russia) chromatograph equipped with
a CR-5 capillary column of a 30 m length and a
0.32 mm diameter coated with a mixture of 5% phe-
nyl- and 95% dimethylpolysiloxane with a film thick-
ness of 0.5 µm. The evaporator temperature was
220°C, and the column temperature was programmed
from 70 to 160°C at a heating rate of 10°C/min. The
flow rate of the carrier gas (nitrogen) was 60 cm3/min.
Due to the absence of the hydrogenation byproducts,
strict correspondence between the volumetrically
measured amount of absorbed hydrogen and degree of
reactant diene conversion calculated from the chro-
matographic analysis data is observed.
For example, COD is hydrogenated to cyclooctene
at a rate that is ten times rate of cyclooctene hydroge-
nation to cyclooctane despite the fact that the double
bonds in the eight-membered cycle are supposedly
equivalent in strain. The observed enhanced reactivity
of the first double bond in hydrogenation can be asso-
ciated with the fact that in the COD molecule (a
“tight” medium-sized cycle), the double bonds of the
opposite sides of the cycle are brought closer together,
and their electrons are capable of interacting with each
other through the ring, which becomes similar to the
interaction of the electrons of conjugated double
bonds, and the main characteristic feature of a system
of conjugated double bonds is that it reacts as a whole.
It was noted [11] that the conjugated system of double
bonds in the COD molecule can be organized as a
RESULTS AND DISCUSSION
The investigation of the hydrogenation reaction of result of the migration of double bonds, i.e., successive
VNB for the purpose of eliminating the possible pro- positional isomerization of these bonds in the hydro-
cess of its polymerization was performed in a solution, genation process due to the isomerizing properties of
where aromatic hydrocarbons were used as a solvent. the palladium catalyst (Scheme 1):
Cat.
Cat.
H2
Cat.
I
II
III
IV
Scheme 1. Hydrogenation of cyclooctadiene-1,5.
The obtained data on the composition of the COD tain only desired cyclooctene. The effect of conjuga-
hydrogenation products (Fig. 1b) are the confirmation
of this route of formation of the conjugated system of
double bonds. Thus, the products of partial hydroge-
nation of COD (a conversion of 20%) contain,
together with cyclooctene (compound 1, Fig. 1b), two
new products (compounds 2 and 3) which are appar-
ently intermediates II and III in Scheme 1. These
compounds are absent in the case of equimolar satura-
tion promotes the enhancement of the electron-
donating properties of the double bond of COD and,
as a result, an increase in the rate of its hydrogenation
in comparison with cyclooctene (Table 1).
In the case of successive saturation of the DCPD
double bonds (Scheme 2), the double bond of the
bicycloheptene (norbornene) moiety of its molecule is
tion of COD with hydrogen, where the products con- hydrogenated first as the most strained and possessing
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872
BERMESHEV et al.
(b)
(a)
(c)
3'
3
2
1
2
3'
2
2'
2'
2'
3
Fig. 2. Chromatograms of VNB hydrogenation products at different conversions: (a) 30%, (b) 110%, (c) 140%. (1) Reactant 5-
vinyl-2-norbornene, (2) endo-2-vinilnorbornane, (2') exo-2-vinilnorbornane, and (3, 3') exo- and endo-isomers of 2-ethylnor-
bornane.
stronger electron-donating properties. The rate of tene moiety of the molecule (Table 1, Scheme 2). It
hydrogenation of the norbornene double bond is was found that there is no isomerization of the double
higher by a factor of 6.7-fold than that of saturation of bonds in the case of hydrogenation of this diene under
the double bond of dicyclopentene in the cyclopen- the given conditions.
10
10
10
1
1
1
2
2
2
9
9
9
H2
H2
7
7
7
8
8
8
6
6
6
3
3
3
5
5
5
4
4
4
2,6
Tricyclo[5.2.1.02,6]decadiene-3,8
Dicyclopentadiene
Tricyclo[5.2.1.02,6]decene-3
Dicyclopentene
Tricyclo[5.2.1.0 ]decane
Dicyclopentane
Scheme 2. Hydrogenation of dicyclopentadiene.
The double bonds of the VNB molecule, like those mixture of the exo- and endo-isomers, with the endo-
in DCPD, are not equivalent in their strain, and the isomer being predominant. The products of partial
saturation of VNB (molar ratio H2 : VNB = 0.3 : 1.0–
1.1 : 1.0) contain two isomers of dihydrovinylnor-
bornene, namely, endo-2-vinylnorbornane (Fig. 2,
compound 2) and exo-2-vinylnorbornane (Fig. 2,
compound 2'). The products of deeper hydrogenation
of VNB (Fig. 2c) obtained at a molar ratio of H2 : VNB
= 1.4 : 1.0 contain the dihydrovinylnorbornene iso-
mers (compounds 2 and 2') and two isomers of tetra-
hydrovinylnorbornene (compounds 3 and 3', the iso-
hydrogenation rate of the double bond in the bicyclo-
heptene part of the VNB molecule is greater by a factor
of 2.6 than that of the double bond of the vinyl group
(Table 1, Scheme 3). It should be noted that under
similar conditions of hydrogenation, the rates of satu-
ration of the double bond in the bicycloheptene moi-
ety of VNB and DCPD molecules are almost the same
(0.021 and 0.019 mol dm−3 min−1, Table 1), i.e., the
reactivity of the double bond is primarily determined
by its nature, not by the structure of the molecule as a mers of 2-ethylnorbornane). The isomerization of the
whole. Vinylnorbornadiene used in the work was a vinyl group to the ethylidene group to form 5-
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SELECTIVE CATALYTIC HYDROGENATION OF ALICYCLIC DIENES
873
Table 2. Yield of desired 2-vinylnorbornane depending on VNB hydrogenation conditions. The catalyst concentration is
4 g/dm3, and the VNB conversion is 100%
2-Vinylnorbornane
Modifying additive
Solvent
T, K
Time, min
yield, %
No additives
Ionol
Toluene
Toluene
333
313
323
333
333
323
90
85.3
88.7
89.0
88.0
85.5
88.1
250 (diff. mode)
90
70
120
110
No additives
Ionol
Pseudocumene
Pseudocumene
ethylidene-2-norbornene or 2-ethylidenenorbornane among the hydrogenation products suggests that
could have proceeded during the hydrogenation pro- either this process did not occur at all (5-ethylidene-2-
cess (Scheme 3). However, the absence of noticeable norbornene is present in insignificant amounts in ini-
amounts of 2-ethylidenenorbornane (less than 1%) tial VNB) or its contribution was insignificant.
H
H
H
H2, Cat.
k1
H2, Cat.
+
+
+
k2
H
H
H
k2 < k1
exo-
endo-
exo-
endo-
exo-
endo-
VNB isomers
2-vinylnorbornane isomers
2-ethylnorbornane isomers
Cat.
Cat.
CH3
H
CH3
H
H2, Cat.
+
+
H
CH3
H
CH3
Z- and E-isomers of 5-ethylidene-2-norbornene
Z- and E-isomers of 2-ethylidene-norbornane
Scheme 3. Hydrogenation of 5-vinyl-2-norbornene.
The process of VNB hydrogenation of under atmo- To achieve a high yield of desired 2-vinylnorbor-
spheric pressure over a finely divided palladium cata- nane in the case of implementation of the VNB hydro-
lyst sharply slows down when the initial cyclodiene is genation process and get more clear differentiation of
completely consumed and degree of conversion of the the rates of saturation of its double bonds, we studied
dihydrovinylnorbornene isomers becomes 40–50% the influence of the nature of the solvent and some
(the conversion with respect to VNB is ≥140%). Such activating additives on the parameters of this process.
a characteristic feature of this process can be explained The obtained results are presented in Figs. 4a and 4b,
if we assume that the isomerizing properties of the pal- and in Tables 1 and 2.
ladium catalyst promote the formation of
2-ethylidenenorbornane as one of the products of the
reaction under study. It is known from the literature
[7] that a trisubstituted double bond of 2-ethylidenen-
orbornane is difficult to hydrogenate, if at all. In this
case, 2-ethylidenenorbornane formed in the mini-
mum (trace) amount can serve as a catalytic poison by
adsorbing on the surface of the catalyst and deactivat-
ing its catalytic sites.
As is seen from the data presented in Fig. 4a, the
rate of hydrogen uptake in the VNB hydrogenation
process depends on the nature of the solvent. In tolu-
ene and pseudocumene, it is almost the same, being
quite high to exceed the rate of the process in the case
of other solvents. The rate of hydrogenation of VNB to
2-vinylnorbornane in aromatic solvents does not
depend on the concentration of VNB in the initial
solution, and the duration of the reaction under the
specified conditions is 100–120 min.
Figure 3 presents VNB consumption and product
buildup rate curves for the VNB hydrogenation pro-
Pseudocumene is the most preferable solvent for
cess. Analysis of the data presented in Figs. 2 and 3 the process of VNB hydrogenation to 2-vinylnorbor-
shows that this process is complex, comprising a num- nane. Its boiling point (168°C) is higher than that of
ber of consecutive and parallel reactions (Scheme 3).
VNB or VNB derivatives. As a result, during the isola-
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874
BERMESHEV et al.
hydroquinone, and 2,6-di-tert-butyl-4-methylphenol
100
90
80
70
60
50
40
30
20
10
(ionol) which are inhibitors of radical chain processes
(including the polymerization process), in an amount
of 5% of the taken catalyst mass.
1
As is seen from the data presented in Fig. 4b, the
use of N,N-dimethyl-p-phenylenediamine and ionol
in the VNB hydrogenation process in aromatic sol-
vents leads to an unexpected increase in the hydrogen
uptake rate, which can result from either the activation
of the catalyst as a result of the modification of its sur-
face or activation of the double bond to be hydroge-
nated. The activating properties of the additives intro-
duced in the specified amount promote an almost
twofold increase in the reaction rate, and, in this case,
the time of VNB hydrogenation to 2-vinylnorbornane
decreases to 60–70 min (Fig. 4b).
2
3'
3
2'
0
0.4
0.8
1.2
1.6
Since fast processes are not always selective, the
influence of the activating additives on the selectivity
for the target product 2-vinylnorbornane was also
studied at 313–323 K. It was found that at this tem-
perature, the use of activating additives, in particular,
ionol, in the VNB hydrogenation process in a
pseudocumene solution with an initial VNB concen-
tration of 30 wt % made it possible to increase the ratio
of the rates of saturation of the double bonds in the
bicycloheptene moiety of VNB and the ethylene bond
of 2-vinylnorbornane from 2.63 to 4.47 (Table 1).
Absorbed hydrogen, mol H2/mol
Fig. 3. Rate curves for the consumption of VNB and the
buildup of products in the VNB hydrogenation process.
The solvent is toluene, C = 4 g/dm , C
and temperature is 333 K. (1) 5-vinyl-2-norbornene,
(2) endo-2-vinylnorbornane, (2') exo-2-vinylnorbornane,
(3, 3') exo- and endo-isomers of 2-ethylnorbornane.
3
3
= 2.2 mol/dm ,
cat
0 VNB
tion of 2-vinylnorbornane from the hydrogenation
products by fractional distillation for further use,
pseudocumene will prevent its possible polymeriza-
tion in the column still.
The result of using the activating additives is an
increase in the total yield of isomeric 2-vinylnorbor-
nanes to 88–89 mol % with the predominant forma-
tion of endo-2-vinylnorbornane and the complete
conversion of reactant VNB (Table 2). The weight
ratio of desired endo- and exo-2-vinylnorbornanes was
about 4 : 1; i.e., endo-2-vinylnorbornane is the main
To stabilize VNB, an unsaturated hydrocarbon
capable of polymerizing during hydrogenation, we
used some functionally substituted aromatic com-
pounds, such as N,N-dimethyl-p-phenylenediamine, product of selective hydrogenation.
2.5
2.0
1.5
1.0
0.5
(a)
(b)
3.0
2.5
2.0
1.5
1.0
0.5
1
3
2
4
2
3
1
4
0
20 40 60 80 100120140
Time, min
0
20 40 60 80 100
Time, min
Fig. 4. Rate curve of hydrogen uptake in the VNB hydrogenation process depending on the nature of (a) solvent ((1) toluene,
(2) pseudocumene, (3) phenylcyclohexane, and (4) 2-propanol) and (b) activating additives ((1) without additives, (2) ionol (sol-
3
vent pseudocumene), (3) ionol, and (4) N,N-dimethyl-p-phenylenediamine (solvent toluene)). C = 4 g/dm , C
=
cat
0, VNB
3
2.3 mol/dm , 333 K.
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SELECTIVE CATALYTIC HYDROGENATION OF ALICYCLIC DIENES
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ACKNOWLEDGMENTS
This work was supported by the Ministry of Educa-
tion and Science of the Russian Federation (unique
project identifier RFMEFI60417X0181, agreement
no. 14.604.21.0181 of September 26, 2017).
Translated by E. Boltukhina
PETROLEUM CHEMISTRY Vol. 58 No. 10 2018