The alkylation of biphenyl over fourteen-membered ring zeolites. the influence of zeolite structure and alkylating agent on the selectivity for 4,4′-dialkylbiphenyl

Article abstract of DOI:10.1246/bcsj.80.1418

Alkylation, i.e. isopropylation, s-butylation, and t-butylation, of biphenyl (BP) was examined over fourteen-mem-bered ring (14-MR) zeolites, CIT-5, UTD-1, and SSZ-53, in order to elucidate the relationships between structure of zeolites and bulkiness of alkylating agents on the shape-selective catalysis. CIT-5 zeolite (CFI) yielded 4,4′-diisopropyl- biphenyl (4,4′-DIPB) in the level of 50-60% in the isopropylation in the range of 150-300°C. 2,2′-, 2,3′-, and 2,4′-DIPB (2,x′-DIPB) isomers were obtained as the predominant DIPB isomers at lower temperatures, and the formation of 3,4′- and 3,3′-DIPB isomers increased with an increase in the temperature. However, the selectivities were in the level of 10- 15% for UTD-1 (DON) and SSZ-53 (SFH) zeolites in the range of 150-350°C. The s-butylation with 1-butene gave results similar to the isopropylation, although the selectivities for 4,4′-di-s-butylbiphenyl (4,4′-DSBB) were higher than those for 4,4′-DIPB at 250 °C: 80-85% for CFI, 40-50% for DON, and 30-40% for SFH. High selectivity for 4,4′-di-f-butylbiphenyl (4,4′-DTBB) was observed in the f-butylation at 250 °C: 95% for CFI, 90% for DON, and 80% for SFH. These differences are due to the spatial difference in their channels, and also due to bulkiness of alkylating agents, propene, 1-butene, and 2-methylpropene. The selectivity for 4,4′- dialkylbiphenyl (4,4′-DABP) was governed by the exclusion of the bulky DABP isomers at the transition state by steric restriction in the zeolite channels.

Full text of DOI:10.1246/bcsj.80.1418

1
418 Bull. Chem. Soc. Jpn. Vol. 80, No. 7, 1418–1428 (2007)
Ó 2007 The Chemical Society of Japan
The Alkylation of Biphenyl over Fourteen-Membered Ring Zeolites.
The Influence of Zeolite Structure and Alkylating Agent
0
on the Selectivity for 4,4 -Dialkylbiphenyl
Yoshihiro Sugi, 1 Hiroyoshi Maekawa, Shafeek Abdul Rashid Mulla, Akira Ito, Chikayo Naitoh,
ꢀ
1
1;
y
1
1
1
1
1;yy
2
2
Kazunori Nakagawa, Kenichi Komura, Yoshihiro Kubota,
Jong-Ho Kim, and Gon Seo
1Department of Materials Science and Technology, Faculty of Engineering, Gifu University, Gifu 501-1193
2School of Applied Chemical Engineering and The Research Institute for Catalysis, Chonnam National University,
Gwangju, 500-757, Korea
Received October 30, 2006; E-mail: ysugi@gifu-u.ac.jp
Alkylation, i.e. isopropylation, s-butylation, and t-butylation, of biphenyl (BP) was examined over fourteen-mem-
bered ring (14-MR) zeolites, CIT-5, UTD-1, and SSZ-53, in order to elucidate the relationships between structure of
0
zeolites and bulkiness of alkylating agents on the shape-selective catalysis. CIT-5 zeolite (CFI) yielded 4,4 -diisopropyl-
0
ꢁ
0
0
0
biphenyl (4,4 -DIPB) in the level of 50–60% in the isopropylation in the range of 150–300 C. 2,2 -, 2,3 -, and 2,4 -DIPB
0
0
(2,x -DIPB) isomers were obtained as the predominant DIPB isomers at lower temperatures, and the formation of 3,4 -
0
and 3,3 -DIPB isomers increased with an increase in the temperature. However, the selectivities were in the level of 10–
15% for UTD-1 (DON) and SSZ-53 (SFH) zeolites in the range of 150–350 C. The s-butylation with 1-butene gave
results similar to the isopropylation, although the selectivities for 4,4 -di-s-butylbiphenyl (4,4 -DSBB) were higher than
ꢁ
0
0
0
ꢁ
0
those for 4,4 -DIPB at 250 C: 80–85% for CFI, 40–50% for DON, and 30–40% for SFH. High selectivity for 4,4 -di-t-
0
ꢁ
butylbiphenyl (4,4 -DTBB) was observed in the t-butylation at 250 C: 95% for CFI, 90% for DON, and 80% for SFH.
These differences are due to the spatial difference in their channels, and also due to bulkiness of alkylating agents,
0
0
propene, 1-butene, and 2-methylpropene. The selectivity for 4,4 -dialkylbiphenyl (4,4 -DABP) was governed by the
exclusion of the bulky DABP isomers at the transition state by steric restriction in the zeolite channels.
Shape-selective alkylation of polynuclear hydrocarbons is a
and/or reaction intermediates are much smaller than the zeo-
lite channels, the reaction is controlled kinetically due to the
reactivity of each position of the reactant at low temperatures
and to the thermodynamic stability of the products at higher
temperatures. These considerations suggest that the extent of
the exclusion by their zeolite channels is an important key fac-
tor in shape-selective catalysis, although it depends on the type
of zeolite. From these points of view, it is interesting to eluci-
date how zeolite structures, particularly, dimensionality, pore-
entrance, and channel, influence the catalysis and how shape-
selective catalysis occurs in zeolites.
promising way to manufacture advanced materials.1–4 We have
previously found that H-mordenite (MOR) was the excellent
catalyst for the shape-selective isopropylation of biphenyl
(
BP) and concluded that shape-selective catalysis occurred
0
0
by predominant formation of 4,4 -diisopropylbiphenyl (4,4 -
DIPB), because of effective exclusion of bulky isomers from
the channels at their transition states.1
–7
Shape-selective catalysis over zeolites occur by differentiat-
ing the reactants, the products, and/or the reaction intermedi-
ates according to their shape and size in sterically restricted en-
vironments of the zeolite.8 The reactant’s fate and the pro-
duct’s formation probability inside the zeolite channels are de-
termined by molecular size and configuration. Only molecules,
of which dimensions are less than a critical size, can enter the
pore and react at the internal catalytic sites, and the bulky
molecules, which can not accommodate inside the channels,
are thus excluded from the channels, resulting in the preferen-
tial formation of the least bulky isomers. Furthermore, only
molecules that can diffuse through the channels will appear
in the products. On the other hand, if reactants, products,
–10
Many researchers have been interested in the synthesis of
new type of zeolites.11 Among them, one-dimensional four-
teen-membered ring (14-MR) zeolites have been found in re-
1
2–16
cent years.
Balkus et al. have synthesized UTD-1 zeolite
(DON),11 which has straight channels (pore-entrance: 0.74
nm ꢂ 0.95 nm) by using bis(pentamethylcyclopentadienyl)-
ꢀ
Wagner et al. have described the synthesis of CIT-5
þ
cobalt(III) cation ([ Cp2Co] ) as structure directing agent
(SDA).
12,13
zeolite (CFI),11 which has slightly corrugated channels (16-
MR cavity with pore-entrance: 0.72 nm ꢂ 0.75 nm), by using
þ
14,15,17
N(16)-methylsparteinium cation ([MeSPA] ) as SDA.
y Present address: Process Development Division, National
More recently, Burton et al. have reported the synthesis of
SSZ-53 zeolite (SFH),11 which has largely corrugated one-
dimensional channels (22-MR cavity with pore-entrance:
0.65 nm ꢂ 0.88 nm), by using [1-(4-fluorophenyl)cyclopentyl-
Chemical Laboratory, Pune 411-008, India
yy Present address: Department of Materials Science and Engi-
neering, Graduate School of Engineering, Yokohama National
University, Yokohama 240-8501
þ
16
methyl]trimethylammonium cation ([4-FPCPMA] ) as SDA.
Published on the web July 11, 2007; doi:10.1246/bcsj.80.1418

Y. Sugi et al.
Bull. Chem. Soc. Jpn. Vol. 80, No. 7 (2007) 1419
Because UTD-1 and SFH-53 zeolites are obtained as their
DIPB isomers was carried out at high sensitivities by duplicate
analyses.
boron versions, the substitution of B3 to Al is necessary for
solid acid catalysis. We are interested in catalytic properties of
these zeolites, particularly in the alkylation of polynuclear
aromatic hydrocarbons.
þ
3þ
Analysis of the encapsulated products in the catalyst used for
the reaction was carried out as follows. The catalyst was separated
by the filtration, washed well with acetone (200 mL), and dried at
ꢁ
1
10 C for 12 h. Resultant catalyst (50 mg) was carefully dissolved
In this paper, we describe the alkylation, i.e., isopropylation,
s-butylation, and t-butylation, of BP over one-dimensional 14-
MR zeolites: CIT-5, UTD-1, and SSZ-53. We also discuss the
in 3 mL of aqueous hydrofluoric acid (47%) at room temperature.
This solution was neutralized with solid potassium carbonate, and
organic layer was extracted three times with dichloromethane
0
0
influence of the selectivity for 4,4 -dialkylbiphenyl (4,4 -
DABP) on the relation between zeolite structure and alkylating
agent in order to elucidate where and how shape-selective ca-
talysis occurs. The results of the 14-MR zeolites were com-
pared to those of H-mordenite with straight channels of pore-
entrance (0.67 nm ꢂ 0.72 nm), which is the most efficient
(
20 mL). After removal of the solvent in vacuo, the residue was
dissolved again in a toluene (5 mL), and subjected to GC and
GC-MS analyses according to the same procedure as the analysis
for bulk products.
The selectivities for ABP and DABP isomers in encapsulated
products were defined in a similar manner as those in the bulk
products. The encapsulated products were also expressed by the
composition of reaction mixtures, because it is difficult to analyze
quantitatively with high reproducibility.
1–7
catalyst for the isopropylation of BP. We focus on the selec-
tivities for DABP isomers to understand shape-selective catal-
ysis in the alkylation by one-dimensional 14-MR zeolites.
Types of zeolites in this paper were abbreviated by framework
type code (FTC) by International Zeolite Association.11
The Characterization of Catalysts. The crystal structure of
zeolites was determined by using powder X-ray diffraction on a
Shimadzu XRD-6000 diffractometer with Cu Kꢀ radiation
˚
Experimental
(ꢁ ¼ 1:5418 A). Elemental analysis of zeolites was performed
by using inductive coupled plasma atomic emission spectroscopy
on a JICP-PS-1000 UV spectrometer (Teledyne Leeman Labs,
Inc., NH, U.S.A.). Crystal size and morphology of the zeolites
were determined on an S-4300 FE-SEM microscope (Hitachi
Corp., Tokyo). Nitrogen adsorption on the zeolite was measured
on a Belsorp 28SA apparatus (Bel Japan, Inc., Osaka). The ad-
sorption of o-xylene was performed by a gravimetric method with
a vapor pressure (0.48 kPa) using a highly sensitive quartz micro-
Zeolites. CIT-5 (CFI) zeolite was synthesized according to the
literature.17 UTD-1 (DON) and SSZ-53 (SFH) were also prepared
from their borosilicates, [B]-UTD-1 and [B]-SSZ-53, respectively,
according to the literature.12,13,16 H-Mordenite (MOR; SiO2/
Al2O3 ¼ 128; TSZ-690HOA) was obtained from Tosoh Corp.,
ꢁ
Tokyo. All zeolites were used as H-forms and calcined at 550 C
before use.
The Alkylation of BP. The alkylation of BP was carried out
in a 100-mL SUS-316 autoclave. Typical reaction conditions of
the isopropylation were: BP 7.71 g (50 mmol), catalyst 0.25 g,
ꢁ
ꢁ
balance at 120 C after evacuation at 550 C. Ammonia tempera-
ture-programmed desorption (NH3-TPD) from the zeolite was
measured using a TPD-66 apparatus (Bel Japan); the catalyst
ꢁ
temperature 150–350 C, and 4 h under a propene pressure of
.8 MPa (0.4 MPa for 1-butene in the s-butylation and for 2-meth-
ꢁ
was evacuated at 400 C for 1 h, and ammonia was adsorbed at
ꢁ
0
1
00 C followed by further evacuation for 1 h. Then, the sample
ylpropene in the t-butylation). An autoclave containing BP and the
catalyst was purged with nitrogen, and heated to reaction temper-
ature. Propene was introduced to the autoclave, and the reaction
was started with agitation. The pressure was maintained constant
throughout the reaction. After cooling the autoclave to ambient
temperature and careful release of excess propene, the catalyst
was separated by the filtration, and the liquid products were sub-
jected to the analyses by using a Gas Chromatograph GC14A or
GC18A (Shimadzu Corp., Kyoto) equipped with an Ultra-1 capil-
lary column (25 m ꢂ 0:2 mm; Agilent Technologies, Inc., MA,
U.S.A.). The products were also identified by using a Shimadzu
Gas Chromatograph-Mass Spectrometer GC-MS 5000.
ꢁ
ꢁ
ꢃ1
was heated from 100 to 710 C at a rate of 10 C min in a helium
flow. The 11B, 27Al, and 29Si NMR spectra of zeolites were record-
ed at room temperature under magic angle spinning (MAS) by
using 7.0 mm diameter zirconia rotors spinning at 4 kHz on an
Inova 400 spectrometer (Varian Corp., MA, U.S.A.).
Results and Discussion
Properties of Zeolites. Typical physicochemical proper-
ties of the zeolites, MOR, CFI, DON, and SFH used for the
catalysis are shown in Table 1. These properties well agreed
to those in the literature.1
3,16,17
Dialkylbiphenyl in the alkylation generally expresses as DABP
in this study. DIPB, DSBB, and DTBB are dialkylbiphenyl isomers
for isopropylation, s-butylation, and t-butylation, respectively.
Yields of each product were calculated on the basis of the
amount of starting BP, and selectivities for each alkylbiphenyl
Figure 1 shows the XRD patterns of calcined CFI, DON,
and SFH. Figure 2 shows typical SEM images of the as-syn-
thesized samples. XRD patterns and SEM images of these zeo-
13,16,17
lites well agreed with those in the literature.
3þ
The substi-
3þ
tution of B in [B]-UTD-1 and [B]-SSZ-53 with Al was
carried out by using 1 M Al(NO3)3 aqueous solution (1 M =
(ABP) and dialkylbiphenyl (DABP) isomers were expressed based
on the total amounts of ABP and DABP isomers, respectively.
ꢃ3
ꢁ
13,16
1
mol dm ) at 80 C according to the literature.
XRD pat-
terns after repeating the substitution three times were almost
the same as original calcined samples. These observations sug-
gest that the structure does not collapse during calcination,
Selectivity for a DABP (ABP) isomer (%)
Each DABP (ABP) isomer (mol)
¼
ꢂ 100:
ð1Þ
DABP (ABP) isomers (mol)
3þ
3þ
acid treatment, and substitution of B with Al .
2
7
Al MAS NMR spectra of calcined CFI, DON, and SFH,
The catalytic activities based on the yield of alkylates were
described in Figs. S1–S6 of Supporting Information. The zeolites
in this study show low activities in some cases such as at low tem-
peratures, or in the t-butylation. In these cases, the analysis for
are shown in Fig. 3. A peak assigned to tetrahedral Al3 spe-
cies, which is incorporated to zeolite framework, was observed
at around 50 ppm for all zeolites. CFI had only tetrahedral
þ

1
420 Bull. Chem. Soc. Jpn. Vol. 80, No. 7 (2007)
Alkylation of Biphenyl over 14-MR Zeolites
Table 1. Properties of Zeolites
Pore
entrance
/nm2
Surface
area
SiO2/Al2O3 /m g
External
surface area volume temperature amount
Pore
NH3 peak
Acid
Channel
structure
2
ꢃ1
2
ꢃ1 a)
ꢃ1
ꢁ
ꢃ1
Zeolite
FTC MR
/m g
/mL g
/ C
/mmol g
0.20
Mordenite MOR 12 Straight with
0:67 ꢂ 0:72
0:72 ꢂ 0:75
128
460
35
38
0.16
389
8-MR side pocket
CFI 14 Slightly
CIT-5
160
339
0.14
294
0.13
corrugated
UTD-1
SSZ-53
DON 14 Straight
SFH 14 Largely
0:70 ꢂ 0:95
0:65 ꢂ 0:88
200
64
403
385
15
83
0.16
0.11
288
316
0.12
0.26
corrugated
a) Calculated from t-plot of N2 adsorption.
MOR
SFH
SFH
DON
CFI
DON
CFI
2
10
20
30
40
50
150
100
50
0
-50
-100
2θ /deg
δ
/ppm
Fig. 1. XRD patterns of 14-MR zeolites (calcined) used as
catalysts.
Fig. 3. 27Al MAS NMR of 14-MR zeolites used as catalysts.
5
µm
2 µm
5 µm
CFI
DON
SFH
Fig. 2. SEM images of 14-MR zeolites (as-synthesized) used for the catalysis.
Al3 species; however, a peak assigned to octahedral Al
þ
3þ
of B
3þ
3þ
with Al
Si MAS NMR spectra.
was also confirmed using the 11B and
2
9
species, which is not incorporated in the framework, also ap-
peared at around 0 ppm upon the substitution of B in the
3þ
The N2 adsorption of CFI, DON, and SFH showed a typical
type-I isotherm (Figure not shown). Specific surface area and
pore volume were 340–400 m g and 0.11–0.16 mL g , re-
spectively. These results indicate that CFI, DON, and SFH
3þ
frameworks of [B]-UTD-1 and [B]-SSZ-53 with Al . These
3
þ
2
ꢃ1
ꢃ1
tetrahedral Al species work as Brønsted acidic sites related
to the catalytic activity in the solid acid catalysis. Substitution

Y. Sugi et al.
Bull. Chem. Soc. Jpn. Vol. 80, No. 7 (2007) 1421
1
1
50
20
MOR
0
.01 mol/m3
DON
SFH
9
6
3
0
0
0
0
SFH
DON
CFI
MOR
CFI
0
5
10
15
20
25
Period /min
Fig. 4. o-Xylene adsorption on zeolites used as catalysts.
1
00
200
300
400
500
600
have typical microporous natures. External surface areas cal-
culated from t-plot of N2 adsorption were 38, 15, and 83
o
Temperature / C
2
ꢃ1
m g for CFI, DON, and SFH, respectively. SFH has higher
external surface area compared to the other two zeolites.
Figure 4 shows the adsorption of o-xylene on CFI, DON,
and SFH. The adsorption was saturated in short period on all
zeolites. It means that their channels are large enough for the
diffusion of o-xylene in them. DON and SFH adsorbed a larger
amount of o-xylene than CFI did; however, the amount of o-
xylene adsorbed on CFI was smaller than those of the MOR.
These differences in N2 and o-xylene adsorption are due to the
difference in their topologies, and should reflect on the catalysis.
TPD profiles of CFI, DON, and SFH are shown in Fig. 5.
Fig. 5. NH3-TPD profiles of zeolites used as catalysts. l-
and h-Peaks by the deconvolution are plotted as dotted
lines.
0
The selectivity for 4,4 -DIPB in the encapsulated products
over MOR maintained high even at high temperatures as 350
C. However, the selectivities for 4,4 -DIPB in bulk products
were as high as 85–90% at low and moderate temperatures be-
ꢁ
0
ꢁ
low 250 C; however, they decreased to 10% with an increase
ꢁ
in the temperature to 350 C These results indicate that the de-
crease in the selectivity over MOR is due to the isomerization
0
0
18
They had l- and h-peaks in the range of 150–200 and 290–
ꢁ
of 4,4 -DIPB to thermodynamically stable 3,4 -DIPB. The
0
3
20 C, respectively. l-Peak is due to physical adsorption of
isomerization of 4,4 -DIPB over MOR occurred at external
acid sites as previously discussed. On the other hand, the se-
3
–7
NH3, and h-peak is assigned to Brønsted acidity, which is re-
lated to acidic sites in acid catalysis. All zeolites have similar
level of acid strength judging from peak temperature of h-peak,
and acid amounts, calculated from area of deconvoluted h-
peak, correspond to the SiO2/Al2O3 ratio (see Table 1). These
zeolites have weaker acidities than MOR; however, their acid-
ities are strong enough for acid catalysis.
0
lectivities for 4,4 -DIPB in bulk products over CFI was also
in the similar level of those in encapsulated products at low
and moderate temperatures. However, they decreased gradual-
ly to around 30% with a further increase in the reaction tem-
ꢁ
perature to 350 C. These differences in the selectivities indi-
0
cate that the isomerization of 4,4 -DIPB proceeds at both ex-
ternal and internal acid sites. These results over CFI show that
The Isopropylation. Figure 6 shows the influence of reac-
tion temperature on the isopropylation over MOR and CFI.
The activities increased with an increase in the temperature
0
its channels are also large enough for the isomerization of 4,4 -
DIPB at the higher temperatures, even if they are small enough
for the predominant formation of 4,4 -DIPB in the isopropyla-
tion of BP. However, there is another possibility that the de-
crease in steric restriction by the CFI channels cause the de-
0
0
for all zeolites. The high selectivity for 4,4 -DIPB, which is
the least bulky isomer among the diisopropylbiphenyl (DIPB)
isomers, was 85–90% over MOR at moderate temperatures
ꢁ
3–7
0
below 250 C as described in previous papers, and 50–60%
ꢁ
cease in the selectivity for 4,4 -DIPB at high temperatures.
0
over CFI up to 300 C. These results show that the shape-selec-
tive catalyses occur inside MOR and CFI channels and that
bulky DIPB isomers are excluded from the channels by the
The isomerization of 4,4 -DIPB inside the channels has also
been observed in the isopropylation over SSZ-24 and
19
20
MAPO-5 (M: Mg and Zn) with AFI topology.
0
0
steric restriction, resulting in the high selectivity for 4,4 -
0
The selectivity for 4,4 -DIPB was less than 20% among
DIPB isomers in the isopropylation of BP over DON and SFH,
as shown in Fig. 7. Over these zeolites, the predominant DIPB
DIPB. The differences in the selectivity for 4,4 -DIPB over
MOR and CFI are due to the difference in the reaction space
inside the channels, because CFI channels are larger than
MOR channels.
0
isomers were the bulky and thermodynamically unstable 2,2 -,
0
0
0
2,3 -, and 2,4 -DIPB (2,x -DIPB) isomers at lower tempera-
0
0
0
Figure 6 also shows the selectivities for 4,4 -DIPB in the en-
capsulated products over MOR and CFI in the isopropylation.
tures, and the yield of thermodynamically stable 3,4 -, 3,3 -,
0
and 4,4 -DIPB isomers increased with an increase in the tem-

1
422 Bull. Chem. Soc. Jpn. Vol. 80, No. 7 (2007)
Alkylation of Biphenyl over 14-MR Zeolites
MOR
CFI
1
00
100
80
60
40
20
0
8
6
4
2
0
0
0
0
0
150
200
250
300
350 150
200
250
300
350
Reaction temperature /°C
Fig. 6. The influence of reaction temperature on the isopropylation of BP over MOR and CFI zeolites. Reaction conditions: for
ꢁ
MOR: BP, 30.84 g (200 mmol), catalyst, 1.0 g; for CFI: BP, 7.71 g (50 mmol); catalyst, 0.25 g; temperature, 150–350 C; propene
0
0
0
0
pressure, 0.8 MPa; period, 4 h. Legends: Bulk products. : 4,4 -DIPB; : 3,4 -DIPB; : 3,3 -DIPB; : 2,x -DIPB; : conversion.
0
Encapsulated products. : 4,4 -DIPB.
DON
SFH
1
00
100
80
60
40
20
0
8
6
4
2
0
0
0
0
0
1
50
200
250
300
350 150
200
250
300
350
Reaction temperature /°C
Fig. 7. The influence of reaction temperature on the isopropylation of BP over DON and SFH zeolites. Reaction conditions: for
ꢁ
DON: BP, 7.71 g (50 mmol); catalyst, 0.25 g; for SFH: BP, 3.86 g (25 mmol); catalyst, 0.125 g; temperature, 150–350 C; propene
pressure, 0.8 MPa; period, 4 h. Legends: see Fig. 6.
0
perature. These results mean that the isopropylation over DON
and SFH is principally controlled kinetically at lower temper-
atures and thermodynamically controlled at high temperatures.
The 2- and 4-positions of BP moieties are preferentially at-
tacked by the alkylating agent under kinetic control, resulting
DON channels are too large to form 4,4 -DIPB shape-
selectively.
0
The selectivities for 4,4 -DIPB in both bulk and encapsulat-
ed products over DON and SFH were around 10–20% in the
ꢁ
range of 150–300 C, as shown in Fig. 7. These results suggest
0
0
in the predominant formation of 2,x -DIPB. The selectivity for
0
that the shape-selective formation of 4,4 -DIPB did not occur
2,x -DIPB decreased with an increase in the temperature under
thermodynamic control accompanied by an increase in the se-
inside the channels of these zeolites. DON and SFH have the
large reaction spaces inside their channels, thus allowing the
formation of bulky DIPB isomers in the isopropylation of BP.
0
lectivity for 3,4 -DIPB. These results indicate that SFH and

Y. Sugi et al.
Bull. Chem. Soc. Jpn. Vol. 80, No. 7 (2007) 1423
MOR
CFI
100
100
8
6
4
2
0
0
0
0
0
80
60
40
20
0
1
50
200
250
300
150
200
250
300
Reaction temperature /°C
Fig. 8. The influence of reaction temperature on the s-butylation of BP over MOR and CFI zeolites. Reaction conditions: for MOR:
ꢁ
BP, 7.71 g (50 mmol); catalyst, 0.25 g; for CFI: BP, 3.86 g (25 mmol); CFI, 0.125 g; temperature, 150–300 C; 1-butene pressure,
0
0
0
0
0.5 MPa; period, 4 h. Legends: Bulk products. : 4,4 -DSBB; : 3,4 -DSBB; : 3,3 -DSBB; : 2,x -DSBB; : conversion.
Encapsulated products. : 4,4 -DSBB.
0
ꢁ
range of 150–300 C, and no significant isomerization of
SFH has larger external surface area compared to the other
zeolites; however, currently, there is no evidence that external
surface area influences the catalytic properties. Detailed stud-
ies are necessary for the clarification.
0
ꢁ
4,4 -DSBB occurred even at the temperature as high as 300 C.
The influence of reaction temperature on the selectivity for
DSBB isomers over DON and SFH is shown in Fig. 9. The se-
0
0
0
0
The s-Butylation. Figure 8 shows the influence of reaction
0
lectivities for 2,2 -, 2,3 -, and 2,4 -DSBB (2,x -DSBB) isomers
decreased with an increase in the temperature from 50 to 20%
for DON and from 62 to 25% for SFH in the ranges of 150–
0
temperature on the selectivity for 4,4 -di-s-butylbiphenyl (4,4 -
DSBB) among di-s-butylbiphenyl (DSBB) isomers in the s-
0
ꢁ
butylation over MOR and CFI. The selectivities for 4,4 -DSBB
0
300 C. The features of the s-butylation resemble those of the
isopropylation over DON and SFH, although the selectivities
for 2,x -DSBB were lower than those in the isopropylation.
were higher than those for 4,4 -DIPB in the isopropylation,
0
0
that is, the selectivity for 4,4 -DSBB was higher than 95% be-
ꢁ
low 250 C for MOR and 80% for CFI in the s-butylation in
However, they are quite different from those over CFI in the
s-butylation. These results mean that the catalyses over DON
and SFH are principally controlled kinetically at lower temper-
atures and thermodynamically at higher temperatures.
ꢁ
0
the range of 150–300 C. The selective formation of 4,4 -
DSBB over MOR and CFI indicates that the s-butylation oc-
curs shape-selectively inside their channels similar to the iso-
propylation. The channels of MOR and CFI can discriminate
0
The selectivities for 4,4 -DSBB in both bulk and encapsulat-
ed products over DON and SFH were 40–50% for DON and
0
0
more effectively 4,4 -DSBB than 4,4 -DIPB from correspond-
ing isomers at their transition states, because the steric restric-
tion of s-butylation by the channels is severer than that of iso-
propylation. The substitution with isopropyl and s-butyl groups
invokes the difference in steric interaction at the transition
states with the channels, although the effective molecular dia-
ꢁ
30–40% for SFH in the range of 150–300 C, as shown in
0
Fig. 9. The selectivities for 4,4 -DSBB should be much higher
than those from equilibrium mixtures estimated from DIPB
isomers.19 These results suggest that DON and SFH channels
have some shape-selective natures for the s-butylation. The
0
0
0
meter of 3,4 -DSBB is almost the same as that of 3,4 -DIPB.
0
channels can enhance the formation of 4,4 -DSBB with a de-
0
3
from the channels compared to 3,4 -DIPB and its bulky isomers.
,4 -DSBB and other bulky isomers are effectively excluded
0
crease in bulky DIPB isomers, such as 2,x -DSBB, because s-
butyl substitution increases the steric restriction at the transi-
tion state of bulky isomers in their channels. However, kinetic
0
Figure 8 also shows the selectivities for 4,4 -DSBB in the
0
encapsulated products in the s-butylation over MOR and CFI.
The selectivity in the encapsulated products over MOR was
higher than 95% even at high temperatures; however, the se-
lectivity in the bulk products decreased from around 90% at
control still contributes to the formation of 2,x -DSBB at
ꢁ
250 C, because these channels cannot effectively exclude
the bulky isomers. The contribution of thermodynamic control
increases with the increase in the temperature, resulting in the
ꢁ
ꢁ
0
2
is due to the isomerization of 4,4 -DSBB to 3,4 -DSBB at the
50 C to 40% at 300 C. These results show that the decrease
0
decrease in the selectivity for 2,x -DSBB and the increase in
0
0
0
the selectivity for 3,4 -DSBB. The selectivities for 4,4 -DSBB
over DON were higher than those over SFH, and the selectivi-
1–7
external acid sites as discussed in the isopropylation. The
0
0
selectivities for 4,4 -DIPB over CFI in bulk products were in
the similar level of those for encapsulated products in the
ties for 2,x -DSBB over SFH were higher than those over
DON. The differences in the selectivities are due to the differ-

1
424 Bull. Chem. Soc. Jpn. Vol. 80, No. 7 (2007)
Alkylation of Biphenyl over 14-MR Zeolites
DON
SFH
1
00
100
80
60
40
20
0
8
6
4
2
0
0
0
0
0
150
200
250
300
150
200
250
300
Reaction temperature /°C
Fig. 9. The influence of reaction temperature on the s-butylation of BP over DON and SFH zeolites. Reaction conditions. for DON:
ꢁ
BP, 3.86 g (25 mmol); catalyst, 0.125 g; for SFH: BP, 3.08 g (20 mmol); catalyst, 0.1 g; temperature, 150–300 C; 1-butene pres-
sure, 0.8 MPa; period, 4 h. Legends: see Fig. 8.
MOR
CFI
1
00
100
80
60
40
20
0
8
6
4
2
0
0
0
0
0
1
50
200
250
300
150
200
250
300
Reaction temperature / °C
Fig. 10. The influence of reaction temperature on the t-butylation of BP over MOR and CFI zeolites. Reaction conditions: for
ꢁ
MOR: BP, 7.71 g (50 mmol); catalyst, 0.25 g; for CFI: BP, 3.86 g (25 mmol); catalyst, 0.125 g; temperature: 150–300 C; 2-meth-
0
0
0
0
ylpropene pressure, 0.5 MPa; period: 4 h. Legends. Bulk products: : 4,4 -DTBB; : 3,4 -DTBB; : 3,3 -DTBB; : 2,x -DTBB;
0
:
conversion. Encapsulated products: : 4,4 -DTBB.
ence in channel structures: straight channels for DON and
corrugated channels for SFH.
The t-Butylation. The influence of reaction temperature
that the t-butylation occurs inside the channels of these zeo-
lites, leading to the selective formation of the least bulky
0
4,4 -DTBB: this is due to severer exclusion of bulky isomers
from bulky alkylating agent at the transition states in their
0
0
on the selectivity for 4,4 -di-t-butylbiphenyl (4,4 -DTBB)
among di-t-butylbiphenyl (DTBB) isomers is shown in
Fig. 10 for MOR and CFI and in Fig. 11 for DON and SFH.
0
channels. The lower selectivities for 4,4 -DTBB over DON
and SFH compared to those over MOR and CFI were due to
the differences in the reaction spaces inside their large chan-
nels. Particularly, corrugated SFH channels afford large reac-
tion space for the catalysis, resulting in the lower selectivity
of around 80%. The catalytic activities in the t-butylation were
0
The selective formation of 4,4 -DTBB was observed over these
ꢁ
zeolites at low and moderate temperatures below 250 C. The
0
selectivities for 4,4 -DTBB were around 95% for MOR and
CFI, 90% for DON, and 80% for SFH. These results indicate

Y. Sugi et al.
Bull. Chem. Soc. Jpn. Vol. 80, No. 7 (2007) 1425
DON
SFH
1
00
100
80
60
40
20
0
80
60
40
20
0
150
200
250
300
150
200
250
300
Reaction temperature / °C
Fig. 11. The influence of reaction temperature on the t-butylation of BP over DON and SFH zeolites. Reaction conditions: BP,
ꢁ
3.86 g (25 mmol); catalyst, 0.125 g; temperature: 150–300 C; 2-methylpropene pressure, 0.5 MPa; period: 4 h. Legends: see
Fig. 10.
lower than those in the s-butylation and the t-butylation over
the zeolites: this may be due to the lower diffusivity of bulky
CFI ꢅ DON > SFH. The differences in the steric restriction
should reflect the difference in the exclusion of bulky DABP
isomers from the channels in the alkylation.
0
4
,4 -DTBB from their channels.
0
The selectivities for 4,4 -DTBB in the encapsulated prod-
ucts in the t-butylation are also shown in Fig. 10 for MOR
Figure 12 shows the selectivity for DABP isomers in the al-
kylation, i.e., isopropylation, s-butylation, and t-butylation, of
ꢁ
and CFI and in Fig. 11 for DON and SFH. The selectivities
0
BP over CFI, DON, SFH, and MOR at 250 C with the alkyla-
for 4,4 -DTBB in the bulk products over MOR, CFI, and
ꢁ
ting agents: propene, 1-butene, and 2-methylpropene. These
selectivities of DABP isomers suggest typical selectivities by
channels of the zeolites, because further isomerization of
SFH were high at the temperatures below 250 C, and they de-
ꢁ
creased significantly at 300 C. However, the selectivities for
0
0
ꢁ
4,4 -DTBB in encapsulated products were around 95% for
MOR, 90% for DON and CFI, and 80% for SFH in the range
4,4 -DABP was almost negligible in the alkylation at 250 C
over these zeolites.
The products in the alkylation of BP are classified to three
ꢁ
of 150–300 C. These results indicate that the decreases in the
0
0
selectivity for 4,4 -DTBB in the bulk products are due to the
isomerization at the external acid sites of MOR, CFI, and
SFH, as discussed in previous sections, because their channels
categories: 4,4 -DABP for the least bulky isomer by the shape-
0
0
0
selective catalysis, 3,x -DABP (3,4 - and 3,3 -) for the thermo-
dynamically stable and bulky isomers under thermodynamic
0
0
0
0
0
are not large enough for the isomerization of 4,4 -DTBB.
0
control, and 2,x -DABP (2,2 -, 2,3 -, and 2,4 -) for the bulky
and thermodynamically unstable isomers under kinetic control.
The selectivities for 4,4 -, 3,x -, and 2,x -DABP highly depend-
ed on type of zeolites and bulkiness of alkylating agents. Par-
ticularly, the selectivities for 4,4 -DABP decreased with an in-
crease in the reaction spaces of zeolites, and increased with an
increase in bulkiness of the alkylating agents. The selectivities
However, no decrease in the selectivity for 4,4 -DTBB in both
0
0
0
bulk and encapsulated products occurred in the t-butylation
over DON even at high temperatures, which may be due to
the low density of external acid sites of DON. However, fur-
ther investigation is necessary for the elucidation of the details.
The Influence of Types of Zeolites and Bulkiness of Al-
kylating Agents. CFI, DON, and SFH have 14-MR pore-en-
trances with different channel structure: CFI has slightly corru-
gated one-dimensional channels with 16-MR cavity (pore-en-
0
0
0
for 3,x - and 2,x -DABP were also influenced by reaction tem-
peratures in addition to type of zeolites and alkylating agents
as discussed in the previous sections. The selectivities for
11,14,15
0
trance: 0.72 nm ꢂ 0.75 nm),
dimensional channels (pore-entrance: 0.74 nm ꢂ 0.95 nm),
DON has straight one-
11–13
4,4 -DABP in encapsulated products were in similar level of
ꢁ
those in bulk products at 250 C, as shown in Fig. 12. These
and SFH has largely corrugated one-dimensional channels
with 22-MR cavity (pore-entrance: 0.65 nm ꢂ 0.88 nm) (see
also Figs. S7–S9 in Supporting Information).11 The differences
in the 14-MR zeolites indicate that the reaction space inside
the channels increases in the order: CFI ꢄ DON ꢄ SFH,
and that the size of pore-entrance increased in the order:
CFI < SFH < DON. These comparisons suggest that the ster-
ic restriction with the channels decreases in the order:
variations of the selectivities by the type of zeolites and alkyla-
ting agents indicate that the alkylation occurs inside the chan-
nels and that the selectivity for DABP isomers should reflect
the differences in the steric restriction inside the channels.
0
The selective formation of 4,4 -DIPB in the isopropylation
was observed only over CFI among the 14-MR zeolites. The
0
selectivity for 4,4 -DIPB over CFI was as high as 54% at
ꢁ
250 C; it is much lower than that over MOR. These results

1
426 Bull. Chem. Soc. Jpn. Vol. 80, No. 7 (2007)
Alkylation of Biphenyl over 14-MR Zeolites
Isopropylation
s-Butylation
t-Butylation
100
100
8
6
4
2
0
0
0
0
0
80
60
40
20
0
MOR CFI DON SFH MOR CFI DON SFH MOR CFI DON SFH
ꢁ
Fig. 12. The selectivity for DABP isomers in the alkylation of BP over the zeolites. Reaction condition: temperature: 250 C.
0
0
0
0
0
0
0
Other conditions: see Figs. 6–11. Legends: : 4,4 -DABP; : 3,x -DABP (3,4 -, 3,3 -, and 3,5-); : 2,x -DABP (2,2 -, 2,3 -,
0
0
and 2,4 -); : 4,4 -DABP in encapsulated products.
mean that CFI channels can exclude the bulky DIPB isomers at
0
selectivities are due to the difference in the structure: straight
channels for DON and corrugated channels for SFH.
The t-butylation of BP over the 14-MR zeolites gave high
the transition state, resulting in predominant formation of 4,4 -
DIPB. However, steric restriction in CFI channels is less se-
vere than that in MOR because CFI has larger reaction spaces
than MOR. On the other hand, DON and SFH gave
0
selectivities for 4,4 -DTBB: 95% for CFI, 90% for DON, and
80–85% for SFH in low and moderate temperatures. These
results indicate that even the large channels of these 14-MR
0
0
0
predominantly 2,x -DIPB at low temperatures and 3,x -DIPB
at high temperatures; however, the selectivities for 4,4 -DIPB
0
zeolites can discriminate 4,4 -DTBB from other bulky DTBB
in both bulk and encapsulated products were 10–15% for
DON and 4–6% for SFH. DON and SFH channels can allow
bulky transition states, leading to predominant formation of
the bulky DIPB isomers; the isopropylation over these zeolites
isomers if the alkylating agent is bulky 2-methyl-2-propene.
The differences in the selectivity among zeolites are caused
by the difference in channel structure as discussed above.
The selectivities for DABP isomers over a zeolite were in-
fluenced by the bulkiness of alkylation agents. The selective
0
can occur under kinetic control to form bulky 2,x -DIPB at low-
er temperatures, as discussed in the previous section. The rapid
0
formation of 4,4 -DABP was observed in the alkylation, i.e.
0
decrease in the selectivities for 2,x -DIPB and the increase in
isopropylation, s-butylation, and t-butylation, of BP over small
CFI and MOR channels. These high selectivities for the least
bulky isomers are due to ‘‘restricted transition state selectivi-
0
0
stable 3,x -DIPB, particularly, 3,4 -DIPB, with an increase in
the temperature, indicate the participation of thermodynamic
control (see also Fig. 7).
1
ty.’’ However, the alkylation over DON and SFH was influ-
enced by the types of alkylating agent: the selectivities for
0
The high selectivities for 4,4 -DSBB were observed in the s-
butylation over MOR and CFI: 95% for MOR and 85% for
CFI. These differences indicate that the steric restriction in
0
4,4 -DIPB in the isopropylation were 20% for DON and
ꢁ
10% for SFH at 250 C. However, the s-butylation gave higher
ꢁ
0
0
the channels of two zeolites for the formation of 4,4 -DSBB
0
selectivities for 4,4 -DSBB at 250 C: 50% for DON and 35%
0
is severer than that of 4,4 -DIPB. On the other hand, the forma-
0
for SFH. However, the selective formation of 4,4 -DTBB
tion of 2,x -DSBB was dominant over DON and SFH at lower
occurred over DON and SFH in the t-butylation. These results
indicate that the channels of these zeolites are too large for the
shape-selective isopropylation, that some shape-selective na-
tures appear in the s-butylation, and that highly shape-selective
catalysis occurs in the t-butylation. Kinetic control at low tem-
peratures and thermodynamic control at high temperatures
contribute to the isopropylation and also to the s-butylation,
temperatures, and it decreased at higher temperatures (see also
Fig. 9), meaning that kinetic and thermodynamic controls still
contribute to the s-butylation. However, the selectivities for
0
ꢁ
4
,4 -DSBB were 47% for DON and 32% for SFH at 250 C,
which are much higher than equilibrium composition of DSBB
isomers estimated from DIPB isomers.19 These results suggest
that DON and SFH also have some shape-selective natures in
0
0
yielding 2,x - and 3,x -DABP as principal products. Effective
exclusion of the bulky DTBB isomers during the t-butylation
occurred even inside large DON and SFH channels, resulting
the s-butylation. The channels can enhance the formation of
0
4
as 2,x -DSBB, because s-butyl substitution increases the steric
,4 -DSBB with a decrease in the bulky DSBB isomers, such
0
0
in the selective formation of 4,4 -DTBB. However, the selec-
0
0
restriction at the transition state of the bulky isomers. The
0
tivities for 4,4 -DSBB and 4,4 -DTBB over SFH were slightly
lower than those over DON. These differences are due to the
differences in channel structure as discussed above. These re-
selectivities for 4,4 -DSBB over DON were higher than those
0
over SFH, whereas the selectivities for 2,x -DSBB over DON
were lower than those over SFH. These differences in the
1
sults indicate that ‘‘product selectivity,’’ in which the least

Y. Sugi et al.
Bull. Chem. Soc. Jpn. Vol. 80, No. 7 (2007) 1427
bulky isomers predominantly diffuse out from the mixtures in-
side the channels, is not operated in these alkylations, because
corrugated zeolites.25 These results also support the above dis-
cussion that the shape-selectivity of zeolites is governed by the
exclusion of bulky isomers at the transition states by steric re-
striction in the channels of the zeolites.
0
the selective formation of 4,4 -DABP was accompanied by
their high selectivities in the encapsulated products. The iso-
0
merization of 4,4 -DABP inside the channels may not be rapid
to establish or approach an equilibrium.
Conclusion
0
The isomerization of 4,4 -DABP occurred in some alkyla-
ꢁ
Alkylation, i.e., isopropylation, s-butylation, and t-butyla-
tion, of BP was examined over the 14-MR zeolites CFI,
tions at high temperatures, such as 300–350 C: isopropylation
over MOR and CFI, s-butylation over MOR, and t-butylation
0
DON, and SFH. CFI yielded 4,4 -DIPB shape-selectively in
the isopropylation. However, the predominant DIPB isomers
over MOR, CFI, and SFH. In these cases, the selectivities
0
0
for 4,4 -DABP in the encapsulated products remained high
even at high temperatures, except in the isopropylation over
were 2,x -DIPB with 2-isopropyl group over DON and SFH,
0
and the selectivities for 4,4 -DIPB were 10–15% in both bulk
0
0
CFI. The isomerization of 4,4 -DABP during the alkylation
and encapsulated products. The selectivities for 4,4 -DSBB
0
occurs at the external acid sites as discussed for the isopropyla-
tion of BP over MOR in previous papers.1 These results show
that the channels of these zeolites are too small for the isomer-
and 4,4 -DTBB were enhanced by using bulky alkylating
agent, 1-butene, and 2-methylpropene, respectively. Particular-
–7
0
ly, 4,4 -DTBB was obtained selectively in the t-butylation over
all zeolites.
0
ization of 4,4 -DABP. However, the isopropylation of BP over
CFI has a different feature among the 14-MR zeolites: the se-
These differences are due to the spatial difference inside
their channels: CFI with slightly corrugated one-dimensional
channels (16-MR cavity with a pore-entrance of 0.72 nm ꢂ
0.75 nm), DON with straight one-dimensional channels (pore-
entrance = 0.74 nm ꢂ 0.95 nm), and SFH with largely corru-
gated one-dimensional channels (22-MR cavity with a pore-
entrance of 0.65 nm ꢂ 0.88 nm). They are also due to bulki-
ness of alkylating agents: propene, 1-butene, and 2-methylpro-
0
lectivities for 4,4 -DIPB in both bulk and encapsulated prod-
ucts in the isopropylation over CFI gradually decreased with
an increase in the temperature, and they decreased to around
ꢁ
3
0% at 350 C. The channels of CFI are large enough for the
0
isomerization of 4,4 -DIPB at both external and internal acid
sites at high temperatures. However, there is another possibil-
ity that the decrease in the steric restriction by CFI channels
0
0
causes a decrease in the selectivity for 4,4 -DIPB at high tem-
pene. The selectivity for 4,4 -DABP was governed by the ex-
peratures. No significant isomerization in the s-butylation and
the t-butylation over DON. This is due to the weak acidity, and
not due to the zeolite structure. However, further research on
these aspects is necessary for full understanding.
We have found the shape-selective formation of 4,4 -DIPB
in the isopropylation of BP over several one-dimensional 12-
clusion of bulky isomers at transition states by the steric re-
striction inside their channels. The exclusion of bulky isomers
from large channels occurs effectively if the transition states
are large enough for the differentiation of the least bulky iso-
mers from the isomers by using bulky alkylating agent, such as
in the t-butylation over DON and SFH.
0
1
–7
MR zeolites with straight channels: H-Mordenite (MOR),
21
ZSM-12 (FTC: MTW),20 SSZ-24 (FTC: AFI), MAPO-5
A part of this work was financially supported by a Grant-in
Aid for Scientific Research (B) 1631005, the Japan Society for
the Promotion of Science (JSPS) and by Research Project
under the Japan-Korea Basic Scientific Cooperation Program,
JSPS and Korea Science and Engineering Foundation
(KOSEF; Grant No. F01-2004-000-10510-0). S. A. R. Mulla
thanks to JSPS for the postdoctoral fellowship.
22
(
FTC: AFI; M: Mg, Ca, Sr, Ba, and Zn), SAPO-5 (FTC:
2
3
24
0
AFI), and SSZ-31. The selectivity level for 4,4 -DIPB
60–90%) reflected the reaction space in the zeolite channels:
(
MOR > SSZ-24, MAPO-5 (M: Mg, Ca, Sr, Ba, and Zn), and
SAPO-5 ꢆ SSZ-31 > ZSM-12. The highly selective forma-
0
tion of 4,4 -DABP has also been observed in the s-butylation
21–23
and the t-butylation over these zeolites.
4
Particularly,
,4 -DSBB and 4,4 -DTBB were selectively obtained over
SSZ-24 and SSZ-31, which have the largest channels among
Supporting Information
0
0
Figures S1–S6: The influences of yields of alkylates in the
alkylation of BP. Figures S7–S9: Images of structure of CFI,
DON, and SFH zeolites. This material is available free of charge
on the Web at http://www.csj.jp/journals/bcsj/.
1
2-MR zeolites.
The selectivities for 4,4 -DIPB over the one-dimensional
0
25
zeolites with corrugated channels, SSZ-55 (FTC; ATS),
SSZ-42 (FTC: IFR), and MAPO-36 (FTC: ATS; M: Mg
and Zn)
25
2
6,27
were around 20–40%. These zeolites have similar
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