Dimerization of norbornene on zeolite catalysts

Article abstract of DOI:10.1016/S1872-2067(14)60251-5

The high activity and selectivity of H-Beta and H-ZSM-12 zeolites in the dimerization of norbornene was established. The norbornene conversion reached 100% in chlorinated paraffin and argon gas medium, with a selectivity of dimer formation of 88%-98%. Four stereo-isomers of the bis-2,2'-norbornylidene structure were identified in the dimer fraction, with the (Z)-anti-bis-2,2′-norbornylidene prevailing over the others. Graphical Abstract The high catalytic efficiency of H-Beta and H-ZSM-12 zeolites in producing bisnorbornylidenes by the dimerization of norbornene gave a norbornene conversion of 100% and a selectivity of dimer formation of 88%-98%.

Full text of DOI:10.1016/S1872-2067(14)60251-5

Chinese Journal of Catalysis 36 (2015) 268–273
a v a i l a b l e a t w w w . s c i e n c e d i r e c t . c o m
j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c h n j c
Article
Dimerization of norbornene on zeolite catalysts
N. G. Grigor’eva*, S. V. Bubennov, L. M. Khalilov, B. I. Kutepov
Federal State Budget Institution of Science, Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, 141 prosp. Oktyabrya, 450075 Ufa,
Russian Federation
A R T I C L E I N F O
A B S T R A C T
Article history:
The high activity and selectivity of H‐Beta and H‐ZSM‐12 zeolites in the dimerization of norbornene
was established. The norbornene conversion reached 100% in chlorinated paraffin and argon gas
medium, with a selectivity of dimer formation of 88%–98%. Four stereo‐isomers of the
bis‐2,2’‐norbornylidene structure were identified in the dimer fraction, with the (Z)‐anti‐bis‐2,2’‐
norbornylidene prevailing over the others.
Received 5 September 2014
Accepted 12 November 2014
Published 20 March 2015
© 2015, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
Published by Elsevier B.V. All rights reserved.
Keywords:
Zeolites
Norbornene
Dimerization
Bisnorbornylidenes
1. Introduction
ReCl5 (Scheme 4) [1,8].
Compound 5 can be synthesized selectively enough with the
The dimers of norbornene are used as a high density rocket
propellant [1]. The norbornene dimer structure is a function of
the nature of the catalyst and the reaction conditions. The pho‐
todimerization of norbornene in the presence of complexes of
Cu(I) leading to the formation of cyclobutane compounds
(Scheme 1) was first reported by Arnold et al. [2].
catalytic complexes developed by a group of Polish scientists
[9–13]. For example, the compounds in question (5) are formed
on the binuclear carbonyl complex of (CO4)W(‐Cl)3W‐
h
This reaction and the structure of the dimers formed under
the influence of Ag(I), Tl(I), and Сu(II) triflates [3] were also
studied by Trecker et al. [4] and Salomon. In the presence of
NiCl2(PPh3)2 and Zn powder in tetrahydrofuran, the reductive
dimerization of norbornene resulted in the formation of the
product 2 (Scheme 2) [5].
+
CuCl2
1a
1b
3%
97%
Scheme 1. Photodimerization of norbornene.
With other Ni‐containing catalysts such as NiCl2L2/NaBH4/
ROH (where L = PPh3, PBu3, Ph2P(CH2)2PPh2) norbornene is
dimerized to give compounds 3 and 4 (Scheme 3) [6,7].
The formation of four bis‐2,2’‐norbornylidene (5) ste‐
reo‐isomers has been detected in the products of metathesis
polymerization of norbornene catalyzed by WCl3, MoCl5, and
Scheme 2. Reductive dimerization of norbornene.
* Corresponding author. Tel: +8‐347‐2842750; Fax: +8‐347‐2842750; E‐mail: ngg‐ink@mail.ru
DOI: 10.1016/S1872‐2067(14)60251‐5 | http://www.sciencedirect.com/science/journal/18722067 | Chin. J. Catal., Vol. 36, No. 3, March 2015

N. G. Grigor’eva et al. / Chinese Journal of Catalysis 36 (2015) 268–273
269
lite (the SiO2/Al2O3 molar ratio of 6.0) synthesized by the tech‐
nique described in Ref. [17]. NH4‐Beta (SiO2/Al2O3 = 18.0),
Н‐ZSM‐5 (SiO2/Al2O3 = 28.4) and NH4 ‐ZSM‐12 (SiO2/Al2O3 =
34) zeolites were manufactured by OJSC “Angarsk Plant of Cat‐
alysts and Organic Synthesis”. The NH4‐Beta and NH4‐ ZSM‐12
zeolite samples were converted into the H form by calcining at
540 °С. Prior to the catalytic runs, the zeolite samples were
thermally treated at 540 °C in air for 4 h.
NiCl2L2 / NaBH4
solvent, 60-80 o
+
C
4
3
Scheme 3. Dimerization of norbornene.
(SnCl3)(CO)3 with a yield of 68% [10].
The catalysts were characterized by X‐ray phase (XRP) and
X‐ray diffraction (XRD) studies, and temperature‐programmed
desorption of ammonia (NH3‐TPD). For the equilibrium ad‐
sorption capacity of the samples by the vapor of water and
benzene at 20 °C, the desiccator technique was used [18].
Heterogeneous catalysts for the oligomerization of nor‐
bornene were less studied. Mobil Oil Corporation has patented
two inventions related to the production of norbornene oligo‐
mers [14,15]. In the patent [14], the synthesis of the nor‐
bornene dimers of structure 1 was performed in the presence
of reduced CrO3 on a large pore silica gel. In patent [15] for the
synthesis of the norbornene dimers of the structure 5, they
proposed the use of zeolites with the pore dimension of 0.5‐0.8
nm of the ZSM family, MCM‐22, PSH‐3, SSZ025, and Beta zeo‐
lite. The norbornene conversion in the presence of ZSM‐5 un‐
der atmospheric pressure and the boiling temperature of the
olefin amounted to 80.7%. 95% of the reaction mixture con‐
tained dimers and trimers formed in the weight ratio of 3.8/1.
It was demonstrated that the heat of combustion of the nor‐
bornene dimers 5 was close to the heat of combustion for
rocket propellant JP‐10, being 41.9 and 39.4 MJ/L, respectively
[15].
However, the reported data did not explain the effect of the
zeolite structure on the catalytic properties and whether the
selectivity of the norbornene dimer formation can be altered by
varying the reaction conditions.
This work reports on the structure effect of Y (FAU‐type),
Beta (BEA‐type), ZSM‐12 (MTW‐type), and ZSM‐5 (MFI‐type)
zeolites as well as the variation of the reaction conditions on
the composition of the norbornene conversion products.
2.3. Dimerization of norbornene
A glass ampoule was loaded with the thoroughly dewatered
solvent, norbornene, and freshly calcined catalyst in the
amount of 10–30 wt% in Ar. The sealed ampoule was placed in
the autoclave and rotated in a furnace controlled at 40–100 °C.
After the suspension was cooled and the catalyst filtered off,
the reaction mixture was obtained followed by the separation
from it of four bis‐2,2’‐norbornylidene isomers by vacuum dis‐
tillation. The conversion of norbornene and composition of the
dimer fraction were determined by gas‐liquid chromatography
using a HRGS 5300 Mega Series «Carlo Erba» chromatograph
with a flame ionization detector. The analysis conditions were:
glass capillary column of 25 m length, SE‐30 phase, tempera‐
ture of analysis 50–280 °C, programmed heating of 8 °C/min,
detector temperature of 250 °C, evaporator temperature of 300
°C, flow rate of helium carrier gas of 30 mL/min. The composi‐
tion of the formed oligomers was analyzed by high perfor‐
mance liquid chromatography (HPLC) using a HP‐1090 in‐
strument. The analysis conditions were: Plgel 100Å polysty‐
rene column, feed toluene flow rate of 0.8 mL/min, the ribbon
speed of 1.5 cm–1, refractive index detector.
2. Experimental
The dimers of norbornene (5a–5d) were identified using
GC‐MS as well as uni‐ and bi‐dimensional NMR spectroscopy.
High resolution mass spectra were recorded using a Fisons
Company instrument. Its chromatograph was equipped with a
DB‐560 capillary quartz column (50 m), the column was heated
from 50 to 320 °C at 4 °C min–1, the electron impact energy was
2.1. Chemicals
For the synthesis, we used freshly distilled norbornene from
Acros Company of 99% purity. The solvents, namely, nonane,
chlorobenzene, methylene chloride, chloroform, carbon tetra‐
chloride, tetrahydrofuran were purified prior to the runs by
standard techniques [16].
70 eV. H and 13С NMR spectra were recorded with a Bruker
1
AVANCE‐400 spectrometer with the working frequency of
400.13 MHz for the 1H nuclei and 100.62 MHz for the 13С nuclei
using standard 5 mm diameter ampoules for solutions of sub‐
stances in CDCl3. Benzene‐d6 and toluene‐d8 were used for the
internal reference. 2D homo‐ (COSY HH) and hetero‐nuclear
(HSQC, HMBS) correlation experiments were performed using
the pulse field gradient techniques.
2.2. Catalysts
The Y, Beta, ZSM‐12, and ZSM‐5 zeolites were studied in
their H form. The HY zeolite with the exchange degree of Na+ to
H+ ions of 96% was obtained by decationating of the NaY zeo‐
.
.
[(CO) ]W(u-Cl) W(SnCl )(CO) ]
3 (2mol%)
4
3
3
+
CH2Cl2, r.t.,24 h
5
68%
Scheme 4. Metathesis polymerization of norbornene.

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N. G. Grigor’eva et al. / Chinese Journal of Catalysis 36 (2015) 268–273
(Z), syn‐Bis‐2,2’‐norbornylidene (5а). b.p. 82–90 °С/5 mm
Hg. H NMR (δ, ppm): 1.15–1.28 (m, 4H, C(6,6’)H2); 1.21–1.35
28.71 (С‐5); 34.93 (С‐7); 35.26 (С‐4); 40.17, 40.31 (2С, C‐3);
40.9, 41.12 (2C, C‐1); 79.71, 80.19 (2C, С‐2). The spectral data
match those given [12,19]. MS m/z: 206.
1
(m, 4H, C(7, 7’)H2); 1.52–1.62 (m, 4H, C(5,5’)H2); 1.58–2.19 (m,
4H, C(3,3’)H2); 2.35 (m, 2H, C(4,4’)H2); 2.62 (m, 2H, C(1,1’)H2);
13C NMR (δ, ppm): 28.55 (C‐5,5’); 28.93 (C‐6,6’); 36.64
(C‐4,4’); 37.08 (C‐3,3’); 39.27 (C‐7,7’); 41.37 (C‐1,1’); 131.44
(C‐2,2’). MS m/z: 188.
3. Results and discussion
3.1. Characterization of the zeolite catalysts
(E), syn‐Bis‐2,2’‐norbornylidene (5b). b.p. 82–90 °С/5 mm
1
Hg. H NMR (δ, ppm): 1.15–1.28 (m, 4H, C(6,6’)H2); 1.21–1.35
The НY, НBeta, НZSM‐12, НZSM‐5 zeolites investigated in
this work were the FAU, BEA, MTW, MFI structural types. They
differed in their crystal structure, framework atom ratio, and
acidic properties. НY and НBeta zeolites possess the largest
pores structure, and НZSM‐5 zeolite has the smallest [20]. The
physicochemical properties of the zeolites studied are given in
Table 1.
According to the XRP and XRD data, and the adsorption
characteristics, all the zeolite samples were characterized by a
crystallinity degree close to 100%. The acidity of the zeolites
obtained by NH3‐TPD showed two peaks characterizing the
“weak” acid sites with the maximum temperature Тmax I at
100–350 °С and the “strong” acid sites with the maximum
temperature Тmax II located above 350 °С (Table 1).
(m, 4H, C(7,7’)H2); 1.52–1.62 (m, 4H, C(5,5’)H2); 1.58–2.19 (m,
4H, C(3,3’)H2); 2.35 (m, 2H, C(4,4’)H2), 2.84 (m, 2H, C(1,1’)H2);
13C NMR (δ, ppm): 28.71 (C‐5,5’); 29.73 (C‐6,6’); 36.78 (C‐4,4’);
37.02 (C‐3,3’); 39.69 (C‐7,7’); 41.87 (C‐1,1’); 131.85 (C‐2,2’). MS
m/z: 188.
(Z), anti‐Bis‐2,2’‐norbornylidene (5c). b.p. 82–90 °С/5 mm
1
Hg. H NMR (δ, ppm): 1.15–1.28 (m, 4H, C(6,6’)H2); 1.21–1.35
(m, 4H, C(7,7’)H2); 1.52–1.62 (m, 4H, C(5,5’)H2); 1.58–2.19 (m,
4H, C(3,3’)H2); 2.35 (m, 2H, C(4,4’)H2); 2.58(m, 2H, C(1,1’)H2);
13C NMR (δ, ppm): 28.59 (C‐5,5’); 29.07 (C‐6,6’); 36.58 (C‐4,4’);
37.16 (C‐3,3’); 39.03 (C‐7,7’); 41.00 (C‐1,1’); 131.54 (C‐2,2’).
(E), anti‐Bis‐2,2’‐norbornylidene (5d). b.p. 82–90 °С/5 mm
1
Hg. H NMR (δ, ppm): 1.15–1.28 (m, 4H, C(6,6’)H2); 1.21–1.35
(m, 4H, C(7,7’)H2); 1.52–1.62 (m, 4H, C(5,5’)H2); 1.58–2.19 (m,
4H, C(3,3’)H2); 2.62 (m, 2H, C(1,1’)H2), 2.80 (m, 2H, C(4,4’)H2);
13C NMR (δ, ppm): 28.66 (C‐5,5’); 29.77 (C‐6,6’); 36.70 (C‐4,4’);
37.04 (C‐3,3’); 39.89 (C‐7,7’); 41.81 (C‐1,1’); 131.95 (C‐2,2’).
Nortricyclane (6). b.p. 35 °С/50 mm Hg. Calculated С7H10
(%): C, 89.29; H, 10.71. Found (%): C, 88.60; H, 11.40. 1H NMR
(δ, ppm): 1.0 (s, 1H, С(3,4,5)H); 1.2 (s, 6H, C(2,6,7)H2); 1.86 (s,
1H, C(1)H); 13C NMR (δ, ppm): 10.3 (C‐3,4,5); 29.9 (C‐1); 33.4
(C‐2,6,7). MS m/z: 94.
The concentration of the important “strong” acid sites
showed its maximum in the HY zeolite sample. On moving to
the НBeta, НZSM‐5, and НZSM‐12 zeolite samples, both the
“strong” acid site concentration and total concentration de‐
creased. The strength of the “strong” acid site in the zeolites
was evaluated by the shift of the high temperature maximum
Тmax (Тmax II = 450 °С) in the thermal desorption. The strength
appeared to be approximately the same for the high silica
НBeta, НZSM‐5, and НZSM‐12 zeolites. The weaker acid sites
present in the HY zeolite (Тmax II = 400 °С) matched the known
reference data [21–23].
1
exo‐2‐Norborneol (7). H NMR (δ, ppm): 1.02–1.05 (m,3H,
C(6)H2, C(7)H2, C(5)H2), 1.12–1.18 (m, 2H, C(3)H2), C(5)H2),
1.36–1.51 (m, 2H, C(7)H2, C(6)H2), 1.62–1.67 (m, 1H, C(3)H2),
2.12–2.35 (m, 2H, C(4)H, C(1)H), 2.81(s, 1H, OH); 3.68 (d, 1H,
C(2)H). 13C NMR, δ: 24.39 (C‐6), 29.27 (C‐5), 34.38 (C‐7), 35.40
(C‐4), 42.37 (C‐3), 44.34 (C‐1), 74.95 (C‐2). The spectral data
match those given [19]. MS m/z: 122. Kovach index Ik 1065.
exo‐, exo‐2,2’‐Dinorbornyl ether (8). b.p. 108 °С/3 mm Hg;
3.2. Effect of the zeolite structure
In the chloroalkane and argon gas medium, the zeolite cata‐
lysts induced the conversion of norbornene into the inner ring
formation product such as nortricyclane (6), and oligomeriza‐
tion products: dimers (5a–5d), and trimers as shown in
Scheme 5.
The catalyst activity was evaluated by the norbornene con‐
version at 60 °C after 5 min (Table 2).
The maximum conversion of norbornene of 80% was ob‐
served on HBeta zeolite. The minimum conversion of 2% was
Т
melt = 55 °С. Calculated C14H22O (%): С, 81.50; H, 11.03; O, 7.47.
1
Found (%): С, 80.12; H, 10.71. H NMR (δ, ppm): 0.94 (d, 1H,
C(6)H2); 1.02 (d, 1H, C(5)H2); 1.04 (m, 1H, C(7)H2); 1.26 (m, 1H,
C(3)H); 1.41 (d, 1H, C(5)H2); 1.46 (d, 1H, C(6)H2); 1.50 (m, 1H,
C(7)H2); 1.50 (m, 1H, C(3)H2); 2.23 (s, 1H, C(4)H); 2.25 (s, 1H,
C(1)H); 3.35 (m, 1H, C(2)H); 13C NMR (δ, ppm): 24.8 (С‐6),
Table 1
Physicochemical properties of the zeolites.
Acidic properties
Concentration of the acid sitesc (mol/g)
Equilibrium adsorption
capacity b
βa
(%) Al2O3 ratio
SiO2/
Sample
Structure
Tmax (°С)
Water
0.28
0.26
0.15
0.05
Benzene
0.32
0.32
0.16
0.20
I
II
250 400
280 450
300 450
300 450
СI
CII
С
HY
НВeta
НZSM‐12
12‐ring; 7.4 × 7.4 Å
100
6
18
34
28
622
530
410
320
560
340
260
300
1182
870
670
620
12‐ring; 5.6 ×5.6 Å; 6.6 × 7.3 Å 100
12‐ring; 5.6 × 6.0 Å 100
НZSM‐5 10‐ring; 5.1 × 5.5 Å; 5.3 × 5.6 Å 100
a crystallinity degree;
b conditions: 20 °C, P/Ps = 0.8;
c СI,CII, and C denote the concentration of “weak” (I), “strong” (II) acid sites and total concentration.

N. G. Grigor’eva et al. / Chinese Journal of Catalysis 36 (2015) 268–273
271
Scheme 5. Norbornene dimerization over a zeolite catalyst in inert medium.
on HZSM‐5 zeolite. Under the action of HY and HZSM‐12 zeo‐
lites, the norbornene conversion reached 68% and 63%, re‐
spectively. At 80 °C reacted for 1 h, the conversion of nor‐
bornene was close to 100% on all catalysts.
The comparison of the results and acidic properties of the
zeolite catalysts allowed us to observe that norbornene was
converted most quickly on HBeta, HY, and HZSM‐12 zeolites
possessing both a high concentration of “strong” acid sites and
wide pores.
The low selectivity of HY zeolite in the reaction of nor‐
bornene dimerization and its specific role in the norbornene
isomerization process may be associated with the heterogene‐
ity of the acidic centers in the catalyst or with the presence of
the active centers promoting the isomerization reaction.
On all the zeolite catalysts, the dimer 5d (57% of the dimer
total) dominated the four isomers, the dimer 5a was the least
(0.7%). This isomer distribution was probably associated with
the higher thermodynamic stability of compound 5d.
The composition of the reaction products including the cy‐
clization‐to‐oligomerization product ratio was also affected by
the structural type. As seen in Table 2, the most selective nor‐
bornene dimer formation occured in the presence of HZSM‐12
(93%–98%) and HBeta (89%–93%) zeolites.
3.3. Effect of the reaction conditions
The inert atmosphere and thorough dewatering of the cata‐
lyst and reagents used are very important for norbornene di‐
merization to occur. In an atmosphere of air, oxygen‐containing
compounds appear in the norbornene conversion products,
namely, 2‐norborneol (7) and dinorbornyl ether (8). In this
case the conversion scheme of norbornene was shown in
Scheme 6.
Evidently, 2‐norborneol (7) is formed as a result of the in‐
teraction of norbornene with water adsorbed in the zeolite. The
dehydration of the norbornyl alcohol or its interaction with
norbornene gives dinorbornyl ether (8) (Scheme 7).
The increasing of reaction time (up to 1 h) and the temper‐
ature (to 80 °C) and the catalyst concentration (to 20 wt%)
resulted in the almost complete conversion of the norbornene,
although the selectivity of the formation of the dimers of nor‐
bornene was decreased.
When using HY zeolite, a significant 40%–43% quantity of
nortricyclane was present in the reaction mixture, and nortri‐
cyclane was the major reaction product on HZSM‐5 zeolite.
What stands out is that on HZSM‐12 and HZSM‐5 zeolites
that belong to the same medium pore pentasil family and pos‐
sessing close acidic properties, different compounds were
prevalent in the reaction products. The major norbornene
conversion product on HZSM‐5 zeolite was nortricyclane (6),
whereas on HZSM‐12 zeolite it was the norbornene dimers.
This may be attributed to the difference in the topology of the
zeolite crystal structure (Table 1). The straight channels
0.56–0.67 nm in diameter in the HZSM‐12 zeolite do not pre‐
vent norbornene dimer formation, whereas in the more tight
HZSM‐5 zeolite channels, the less bulky nortricyclane mole‐
cules were formed and diffuse more easily than the norbornene
dimer molecules. The diffusion of the latter was more difficult.
The comparison of the results obtained with the zeolite Beta
and ZSM‐12 showed the high efficiency of these catalysts in the
Table 2
Dimerization of norbornene in the presence of the zeolite catalysts.
Reaction time
Selectivity (%)
5a–5d
58
Catalyst loading
T
(°C)
60
60
60
60
60
80
60
80
Conversion
Catalyst
(min)
5
5
5
(wt%)
10
10
10
10
10
20
10
(%)
68
80
63
2
93
100
78
97
6
40
4
2
98
4
5
2
4
Trimers
HY
HBeta
HZSM‐12
HZSM‐5
HBeta
HBeta
HZSM‐12
HZSM‐12
2
3
—
—
6
6
3
3
93
98
2
90
89
95
93
5
60
60
60
60
20
Reaction conditions: CH2Cl2 solvent, the initial concentration of norbornene in the solvent [М0] = 3.5 mol/L.

272
N. G. Grigor’eva et al. / Chinese Journal of Catalysis 36 (2015) 268–273
7
Cl
Cl
1
O
1
OH
6
2
2
6
+
5a-d
4
6
+
4
+
zeolite
3
5
5
3
5a-5d
+
+
7
8
Scheme 6. Conversion of norbornene over zeolite catalysts in air.
81%
17%
Scheme 8. Tranformation of norbornene on HBeta zeolite in chloro‐
benzene.
O
OH
2
-H O
2
OR
zeolite
+
ROH
OH
+
97-100%
R = Me, Et, Pr, Bu, Hex, Oct, Cyclohexyl, Benzyl
Scheme 7. Conversion of norborneol over zeolite catalysts.
Scheme 9. Interaction of norbornene with alcohols over zeolite cata‐
lysts.
synthesis of the dimers (5). It should be noted that the selectiv‐
ity of the formation of dimers (5) in the presence of zeolite
HBeta and HZSM‐12 exceeded the selectivity attained by the
action of metal complex catalysts [10].
Beside the oligomerization of norbornene in chlorobenzene,
the formation of chloronorbornylbenzenes was also observed
(Scheme 8).
The aliphatic alcohols ROH were reagents as well. Therefore
alkoxynorbornanes were the major reaction products (Scheme
9).
The conversion of norbornene in isooctane in the presence
of the catalysts occurred with the formation of nortricyclane
and oligomers. Dimers dominated among the latter in the
amount of 75%–95%.
The comparison of the runs showed that the most selective
norbornene dimer formation occurred in chloroalkanes (Table
2, 4).
Similar to the reaction in the atmosphere of Ar, the highest
60%–73% yield of the norbornene dimers was obtained on the
HZSM‐12 and HBeta zeolites. On the HY and HZSM‐5 zeolites,
the isomerization of norbornene occurred resulting in the for‐
mation of nortricyclane in the yield amounts of 60% and 66%,
respectively.
The yields of the alcohol (7) and ether (8) were markedly
increased when water was added into the reaction mixture in
the amount of ~1 mol per 1 mol of norbornene (Table 3).
In this case, the maximum activity was with the НBeta zeo‐
lite where the norbornene conversion was ~100%, and the
selectivity of dinorbornyl ether formation was 99.3%. The
transformation of norbornene in the presence of the zeolite
catalysts was studied not only in chloroalkanes (ССl4, CHCl3,
CH2Cl2), but also in other solvents, namely, chlorobenzene, iso‐
octane, and aliphatic alcohols (Table 4).
4. Conclusions
From studies of the catalytic properties of НY, НBeta,
НZSM‐12, and НZSM‐5 zeolite catalysts that differ in structure
Table 3
Interaction of norbornene with water on the zeolites.
Selectivity (%)
7
Catalyst loading
Reaction time
T
(°C)
60
60
60
60
Conversion
Catalyst
(wt%)
20
20
20
(h)
1
1
1
(%)
17
100
50
5
6
27
1
19
37
8
5а–5d
—
—
4
—
HY
18
—
4
55
99
73
38
HBeta
HZSM‐12
HZSM‐5
50
10
25
Table 4
Transformations of norbornene in different solvents.
Selectivity (%)
Catalyst loading
T
Conversion
Catalyst
Solvent
(wt%)
10
10
30
10
10
30
(°C)
100
80
80
40
(%)
90
96
99
100
94
100
6
5а–5d
41
Trimers
Pr
—
17
—
100
—
HY
isooctane
chlorobenzene
isooctane
methanol
isooctane
57
—
15
—
19
6
2
2
HBeta
HBeta
HBeta
HZSM‐12
HZSM‐12
81
74
—
77
11
—
4
100
40
carbon tetrachloride
88
6
—
Reaction conditions: initial concentration of norbornene in the solvent [М0] = 3.5 mol/l, reaction time 1 h; Pr—Products of the interaction norbornene
with the solvent.

N. G. Grigor’eva et al. / Chinese Journal of Catalysis 36 (2015) 268–273
273
Graphical Abstract
Chin. J. Catal., 2015, 36: 268–273 doi: 10.1016/S1872‐2067(14)60251‐5
Dimerization of norbornene on zeolite catalysts
N. G. Grigor’eva*, S. V. Bubennov, L. M. Khalilov, B. I. Kutepov
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, Russian Federation
The high catalytic efficiency of H‐Beta and H‐ZSM‐12 zeolites in producing bisnorbornylidenes by the dimerization of norbornene gave a
norbornene conversion of 100% and a selectivity of dimer formation of 88%–98%.
Сatal A, 2005, 226: 259
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and acidic properties, the high activity and selectivity of НBeta
and НZSM‐12 zeolites for norbornene dimerization was found.
The selectivity for the bis‐2,2’‐norbornylidene dimer structure
formation reached 88%–98%. Among the four stereoisomers of
bis‐2,2’‐norbornylidene, the fraction of (E), anti‐bis‐2,2’‐nor‐
bornylidene, was 57%. This was probably due to the higher
thermodynamic stability of the compound. In a reaction me‐
dium containing water vapor, norbornene formed norbornyl
alcohol and dinorbornyl ether. The solvents most suitable for
the selective production of norbornene dimers are the chlorin‐
ated paraffins, namely, methylene chloride, carbon tetrachlo‐
ride, or chloroform.
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