CHEM. RES. CHINESE UNIVERSITIES Available online at www.sciencedirect.

com
2008,24(2), 175-179
Article ID 1005-9040~2008~-02-175-05 ScienceDirect

Diels-Alder Addition of Dicyclopentadiene with

Cyclopentadiene in Polar Solvents
ZHANG Xiang-wen, JIANG Qiang, XIONG Zhong-qiang,
ZOU Ji-jun*, WANG Li and MI Zhen-tao
Key Laboratory for Green Chemical Technology of Minishy of Education, School of Chemical Engineering
and Technology, Tianjin Universiv, Tianjin 300072, f? R. China

Abstract Diels-Alder addition of dicyclopentadiene and cyclopentadiene in polar solvents has been studied to produce
tricyclopentadiene(TCPD) that is a potential high-density fuel precursor. GC and MS analysis shows that the adducts
contain two isomers, namely exo- and endo-TCPD. Theoretical simulation shows that although the transition state of
endo-TCPD has a lower activation energy, exo-TCPD is thermodynamically preferred. Polar solvents can accelerate the
reaction rate and improve the exolendo ratio of TCPD because the transition state of exo-TCPD has a higher polarity
than that of endo-TCPD. The solvent effect follows the order of polarity: benzyl methanol>cyclohexanone>toluene. The
conversion rises when the temperature ranges from 120 to 150 "C, but the selectivity of TCPD slightly decreases.
Increasing the pressure can improve the conversion but the exolendo ratio of TCPD is unchanged. The apparent kinetics
in different solvents was determined via nonlinear regression. The activation energies are 99.47, 101.15, and 107.32
kJ/mol for benzyl methanol, cyclohexanone, and toluene, respectively. The optimal reaction conditions are as follows:
benzyl methanol as solvent, temperature 150 OC, and pressure 900 kPa. After an 1 I-hour reaction, a conversion of 58.0%,
a TCPD selectivity of 95.7%, and an exolendo ratio of 16.3 has been obtained.
Keywords High density fuel; Dicyclopentadiene; Cyclopentadiene; Diels-Alder addition; Solvent effect

1 Introduction also be considered for large-scale application.

High-density fuel(HDF) with high density and
volumetric energy content(or heating value) can
provide more propulsive energy for aircrafts than
traditional aviation kerosene derived from refinery.
For volume-limited aircrafts, the replacement of tradi-
tional fuel with HDF can significantly increase flight
distance and payload. The preparation of HDF has
attracted increasing interest. However, these fuels are
not naturally obtained and have to be artificially
synthesized. Besides high density, the general re-
quirements for HDF are low viscosity, low freezing
point, and acceptable flash point"321. With these
considerations, the structure of candidate fuels has to
be properly chosen. Polycyclic hydrocarbons(with
tri- and tetra-cycles) are suitable candidates because of
their high density. But the molecular stereo-configu-
ration needs to be controlled to provide acceptable
freezing point. In addition, the preparation cost should
Dicyclopentadiene(DCPD) and its monomer
cyclopentadiene(CPD)are the major by-products from
steam cracking of naphtha and thus can be easily ob-
tained for large-scale production with low-cost. They
are ideal feedstock for the preparation of HDF. In fact,
em-tetrahydrotricyclopentadienederived from DCPD
and CPD has been regarded as a very promising HDF.
It can be prepared via the Diels-Alder addition of
DCPD with CPD, hydrogenation, and isomerization(if
ne~essary)[~-~]. In this process, the Diels-Alder reac-
tion is the key step to produce a suitable HDF precur-
sor. The polymerization of DCPD has been widely
studied to synthesize polymers"381. However, the
DCPD/CPD Diels-Alder addition has not been studied
in details. In this article, we studied the reaction to
improve the reaction rate and control the stereo-
configuration of adducts, with the purpose of synthe-
sizing a high density fuel with a low freezing point.

*Corresponding author. E-mail: jj-zouchem@yahoo.corn.cn

Received April 2, 2007; accepted October 18, 2007.
Supported by Fundamental Research Project of Commission of Science, Technology and Industry for National Defense of
China(No.Al420060 192).

Copyright Q 2008, Jilin University. Published by Elsevier Limited. All rights reserved.
176 CHEM. RES. CHINESE UNIVERSITIES
2 Experimental
Commercially obtained DCPD(Yang1i Petro-
chemical Co., Hangzhou, China) was purified by va-
cuum distillation, and the purity was >99.7%. Cyclo-
pentadiene was prepared before reaction through the
decomposition of DCPD at atmospheric pressure, and
the purity was >95.6%. The solvents, including benzyl
methanol, cyclohexanone, and toluene(ana1ytic purity)
were used as received without any treatment.
The Diels-Alder addition reaction was carried out
in a 250 mL mechanically agitated reactor(Xintai
Chemical Equipment Co., Weihai, China) made of
316 stainless steel equipped with an external band
heater. The error of reaction temperature was con-
trolled within h1 K by regulating the input power. To
conduct the reaction, 100 mL of reactant mixture such
as DCPD/CPD(molar ratio 1:l) or DCPD/CPD/
solvent(mo1ar ratio 1:1:2) was introduced into an au-
toclave, sealed, and flushed with nitrogen. Then it was
heated to defined temperature at a low agitation speed
of 100 r/min. After that the agitation speed was
quickly increased to 720 r/min, and it was regarded as
the beginning of the reaction. The reaction pressure
was controlled by adjusting the pressure of nitrogen.
The reaction mixture was taken out at regular intervals
for analysis.
The composition of the reaction mixture was
analyzed by a GC-MS(HP5890II-HP597 1A) equipped
with a HP-1 capillary column(l2 mx0.22 mm). The
concentrations of the synthesized organics were ana-
lyzed by a GC(HP-4890) equipped with FID detector
and HP-5 capillary column(30 mx0.53 mmx0.15 pm).
Their concentrations were determined through area
normalization method because these compounds have
very similar response factors.
The individual conversion of CPD or DCPD was
difficult to define because CPD could transfer to
DCPD via dimerization, and DCPD could transfer to
CPD through dissociation. Therefore, a total conver-
sion of CPD and DCPD was defined as follows:
Conversion(%)=( [DCPD]ix2+[CPD]i)/([DCPD],x
2+[CPD],)x 100%
where [AIi and [A], mean the initial and final concen-
trations of A, respectively. The selectivity and yield of
TCPD were defined as follows:
Selectivity(%)=[TCPD],x 3/( [DCPD]ix2+[CPD]i-
[DCPD],x2-[ CPD],)x 100%
Vo1.24
Yield(%)=[ TCPD],x 3 4[DCPD] x 2+ [CPDIi) x 100%
Theoretical simulations were performed with the
Gaussian03 series programs[']. Full structure optimi-
zation was done at density functional theory(DFT)
level with B3LYP/6-3 lG* basis sets"']. The total
energies were corrected for scaled zero point vibra-
tional energies(ZPE's) with a factor of 0.9804"'].
Transition state structures were located with STQN
method in QST3 procedure"21.
3 Results and Discussion
3.1 Product Analysis and Reaction Mechanism
GC-MS analysis indicates that the resulting
products include two isomers of TCPD and a few
tetra- and pentamers. When heated, CPD molecules
are added to DCPD molecules through Diels-Alder
[4+2] cycloaddition to produce TCPD molecules.
DCPD+CPD +TCPD (1)
In this reaction, DCPD molecules serve as the di-
enophile and CPD as the diene. Dicyclopentadiene have
two bonds, one in the cyclopentene ring(CP-bond) and
the other in the norbornene ring(NB-bond). CPD mole-
cules may be added on either of these two bonds.
Moreover, DCPD molecules have two different stereo-
configurations, which may lead to different isomers for
the adduct products. Theoretically, there are eight
stereo-configurations for TCPD. However, the feed-
stock DCPD are predominantly composed by endo-
i~omer(>96%)"~]. Furthermore, the studies on the hy-
drogenation of DCPD have shown that the NB-bond is
much more reactive than the C P - b ~ n d " ~Therefore,
~. the
Diels-Alder addition should mainly occur in the nor-
bornene ring, and the produced TCPD should have two
configurations as shown in Scheme I, which is in good
agreement with the MS analysis.
w
entio-rxo-endo
Scheme 1 Diels-Alder addition of cyclopentadiene
with dicyclopentadiene
The formed TCPD can further react with CPD to
produce oligomers with multi-rings.
TCPD+CPD -TeCPD+CPD --,PCPD (2)
GC analysis shows the former peak of TCPD
eluted is much smaller than that eluted latter, with a
No.2 ZHANG Xiang-wen et al. 177
ratio of 1:6.4 of them. It has been widely accepted that Therefore, it is possible to increase the selecti-
Diels-Alder reaction follows the endo principle, that is, vity of exo-isomer if the reaction conditions are
the reaction is controlled by dynamics and endo- properly controlled.
adduct is the major product. It can be reasonably con-
cluded that the former GC peak is em-exo-endo 3.2 Effect of Solvent
TCPD(exo-TCPD), whereas the latter is endo-exo- For Diels-Alder reaction, solvents may have im-
endo TCPD(endo-TCPD). For liquid fuel, the exo- portant effects on the reaction rate and stereo-con-
configuration is more desired because it has a low figuration of ad duct^"^-'^'. So the effects of solvents,
freezing point and a low viscosity after hydrogena- including benzyl methanol, cyclohexanone, and tolu-
tionll,21. Becase the reaction product has a very low ene were studied. Their polarity decreases as follows:
concentration of em-isomer, it is necessary to im- benzyl methanol>cycIohexanone>toluene. Table 2
prove the exo/endo ratio of TCPD. shows that the presence of solvent slightly depresses
To study the possibility to increase exo-configu- the conversion, probably because the concentrations
ration by adjusting the reaction conditions, a simple of reactants are dramatically decreased. The conver-
DFT calculation was conducted. The optimized mo- sion rises up with the increase of solvent's polarity,
lecular structures of reactants, products, and transition indicating that polar surroundings accelerate the reac-
states are shown in Fig.1. Their corresponding para- tion. Table 2 also shows that the utilization of solvent
meters are shown in Table 1. The transition state of can improve the percentage of exo-TCPD. The
endo-TCPD has a lower activation energy, indicating exdendo ratio is increased with increasing solvent
that the Diels-Alder addition reaction is controlled by polarity. The ratio is 15.3 in benzyl methanol, signi-
dynamics and endo-isomer is the preferred product. ficantly higher than the case without solvent( 1:6.4).
This is in agreement with the experiment result men- Table 2 Effects of solvents on addition reaction
tioned above. However, the total energy of exo-TCPD exo/endo ratio
Solvent Conversion(%) Yield(%)
ofTCPD
is lower than that of endo-TCPD, indicating that Benzyl methanol 52.7 50.2 1:5.3
em-isomer is more stable in thermodynamics. Cyclohexanone 49.9 47.4 1:5.6
Toluene 42.3 39.9 1:5.8
None 53.9 51.7 116.4

As shown in Table 1, the dipole moment of

CPD - DCPD
em-TCPD is larger than that of endo-TCPD. Fur-
thermore, em-TS has a significantly larger dipole
moment than endo-TS. These results clearly indicate
that polar environment prefers em-TCPD rather than
- -
endo-TCPD because polar solvent can stabilize
endu-exu-endu-TCPD em-exo-enduITCPD em-TS and reduce the reaction free energy. This con-
A
firms that the polar solvent can increase the selectivity
of exo-TCPD. Among the three solvents studied, ben-
zyl methanol has the strongest polarity, so its effect is
more obvious than the others.
endu-exo-endu-TS exu-exu-endo-TS
3.3 Effects of Temperature and Pressure
Fig.1 Optimized structures of reactants, products
and transition states Fig.2 shows that increasing the reaction tempe-
Table 1 Calculated parameters of reactants, rature can promote the conversion. At 120 "C, the
products and transition states
Conversion is below 10%. With the increase of tem-
Species Eta,/a.u. AEJ(kJ.mol-') Dipole/Deby
CPD -194,007486 - 0.4275
perature, the conversion quickly rises up, and a con-
DCPD -388.033985 - 0.0969 version of 50% is obtained at 150 "C. In a temperature
endo-TCPD -582.073928 - 0.05 16 range of 120-150 OC, the selectivity of TCPD is only
exo-TCPD -582.073973 - 0.4057 slightly decreased, indicating that the formation of
enda-TS -582.0023 13 123.48 0.3745 higher polymers is not markedly accelerated. Increa-
exa-TS -58 1.99658 1 138.48 0.5306
sing temperature also slightly improves the exdendo
178 CHEM. RES. CHINESE UNIVERSITIES
ratio of TCPD but the effect is limited. With the fur-
ther increase of temperature, the formation of higher
polymers is rapidly increasedi6].The side-products are
difficult to separate and seriously deteriorate the
property of final product, so the side-reactions have to
be avoided by controlling the temperature below
150 "C.
I I I I I I
120 125 130 135 140 145
TemperatureK
I I I I I I
120 125 130 135 140 145 150
TemperatureK
Fig.2 Effect of reaction temperature on conversion(A)
and selectivity(B) of addition reaction
a. Benzyl methanol; b. cyclohexanone;c. toluene.
Reaction pressure can also influence the addition
reaction. Because the boiling point of CPD is very
low(40 "C), most of it will leave off from the liquid
when heated. This induces a low concentration of
CPD in the liquid phase and thereby reduces the pos-
sibility of addition reaction. Therefore, a high pressure
is needed to keep the CPD in the liquid phase. As
shown in Fig.3, the conversion is increased with the
increase of pressure. But reaction pressure has no ef-
fect on the exo/endo ratio of TCPD.
I I I 1
0 200 400 600 800
pkPa
Fig3 Effect of reaction pressure on addition reaction
a. Benzyl methanol; b. cyclohexanone;c. toluene.
Vo1.24
3.4 Reaction Kinetics
The apparent reaction kinetics was analyzed in a
temperature range of 120-150 "C at a pressure of
100 kPa. Fig.4 shows the molar fraction-time data in
benzyl methanol that will be used for kinetics analysis.
The molar fraction of TCPD always increases with
time on its stream, and high temperature leads to more
TCPD produced. However, the tendencies for CPD
and DCPD are different. The molar fraction of CPD
declines quickly within 2 hours and slowly decreases
thereafeer. Correspondingly, the molar fraction of
DCPD accumulates rapidly in the first 2 hours and
then slowly increases. This tendency indicates that, at
150 the beginning of the reaction, most of CPD is trans-
formed to DCPD via dimerization reaction because of
its high concentration. After that, the dimerizaiton of
CPD and dissociation of DCPD reaches equilibrium,
and Diels-Alder addition is the major reaction. At a
higher temperature, the addition reaction is improved,
so the highest DCPD molar fraction is reduced. Simi-
lar tendencies were also observed in cyclohexanone
and toluene. The highest DCPD molar fraction de-
clines with the increase of solvent's polarity, con-
firming that polar solvent can accelerate the addition
reaction.
0 100 200 300 400 500 600 700
Time/niin
Fig.4 Concentration-time data of addition reaction
with benzyl methanol as solvent
-A-l20 'c; -B- 130 "C; -0- 140 'c; -V- 150 "c.
The power-law reaction kinetics can be ex-
pressed as follows:
r = d[TCPD1 = k[CPDIm[DCPD]"
dt
k = k, exp(-E, / RT)
The reaction rate is obtained by fitting the molar
fraction-time data of TCPD using cubic polynomial
1000
model and then by differentiating at each experimental
point. The kinetics parameters were calculated by
multi-elements linear regression. The result shows a
No.2 ZHANG Xiang-wen et al.
good reliability with the correlation coefficient above
0.94. As shown in Table 3, the reaction order
respecting to CPD is much higher than that respecting
to DCDP, indicating that the Diels-Alder addition is
greatly dependent on CPD concentration. This con-
firms that increasing pressure can improve the reac-
tion because of higher CPD concentration in the liquid.
It is noted that the activation energy for benzyl me-
thanol is the lowest, whereas that for toluene is the
highest. This clearly shows that polar solvent can ac-
celerate the addition reaction.
Table 3 Kinetics parameters for addition reaction
in different solvents
Polar solvent m n Ro E,l(kJ.mol-')
Benzyl methanol 1.1169 0.7247 2.12X 10'" 99.47
Cyclohexanone 1.1984 0.5952 2.62X 10'" 101.15
Toluene 2.4066 0.6914 1.19X lo9 106.24
4 Conclusions
The Diels-Alder addition of DCPD with CPD
has been studied with the purpose of preparing a high
density fuel precursor. The adducts contain exo-
exo-endo and endo-em-endo TCPD, with the latter as
the major product. Polar solvents can improve the
reaction rate and increase the exolendo ratio of
TCPD. The solvent effect follows the polarity order
of solvents: benzyl methanol>cyclohexanone>
toluene. Increasing temperature can accelerate the
reaction, but it should not exceed 150 "C. Reaction
pressure also shows a positive effect on the reaction.
The exdendo ratio of TCPD is not influenced by
179
temperature and pressure. The apparent kinetics
analysis shows that the reaction in benzyl methanol
has the lowest activation energy of 99.47 kT/mol.
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