Catalysis Communications 8 (2007) 1759–1762

www.elsevier.com/locate/catcom

Synthesis of dioctyl phthalate using acid functionalized

ionic liquid as catalyst
Hongliang Li a, Shitao Yu a,*
, Fusheng Liu a, Congxia Xie b, Lu Li a

a
College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
b
College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

Received 8 November 2006; received in revised form 19 January 2007; accepted 20 January 2007
Available online 1 February 2007

Abstract

Dioctyl phthalate were synthesized by using acid functionalized ionic liquid as catalyst. The results indicated that HSO3-functional-
ized Brønsted acidic ionic liquids show better catalytic and reusable performance than non-functionalized ionic liquids or the combina-
tion of neutral ionic liquids and Brønsted acid. Under the optimum conditions, using 1-methyl-3-(3-sulfopropyl)-imidazolium hydrogen
sulfate as catalyst, the conversion of phthalic anhydride was 98%. After easily separated from the products the ionic liquid could be
reused 8 times without any disposal, and the conversion of phthalic anhydride was not less than 95%. Therefore, an environmental
friendly approach for the synthesis of dioctyl phthalate is provided.
Ó 2007 Elsevier B.V. All rights reserved.

Keywords: Functionalized ionic liquid; Esterification; Catalyst; Dioctyl phthalate

1. Introduction of scholars from various fields such as synthesis, catalysis,

Dioctyl phthalate (DOP) is a kind of widely used plasti-
cizer. The catalysts used in traditional synthesis process of
DOP were mainly sulfuric acid, titanate and solid acid. The
sulfuric acid cannot be reused and have other disadvan-
tages such as equipment corrosion, more byproducts,
tedious workup procedure and environmental problem.
Also, the titanate [1] is of some disadvantages of higher
cost, difficult separation from products and more con-
sumption of energy. Although, solid acid [2,3] catalyst
can overcome some of above-mentioned shortcomings, it
has its own disadvantages such as easily deactivation, oper-
ation loss and high mass transfer resistance, therefore its
application is limited.
The room temperature ionic liquid, a kind of environ-
mental friendly solvent and catalyst, due to its adjustable
physical and chemical properties, got broadly attention
*
Corresponding author. Fax: +86 532 84022719.
E-mail address: yushitaoqust@126.com (S. Yu).
separation and electrochemistry [4]. In recent years,
research of ionic liquids is focused on functionalized ionic
liquids (FIL), which can provide better specialized func-
tions with functional group linked with its cation or anion.
Since 2002, Cole et al. [5] first published a article about
sulfonic FIL with strong Brønsted acidity, the research
and application of various FILs have received more and
more attention [6,7]. Among them there were many arti-
cles on the subject of FIL used in different esterifications
[8,9], but to the best of our knowledge, no articles about
synthesis of dioctyl phthalate using FIL has been
published.
In this paper, we prepared several HSO3-functionalized
Brønsted acidic ionic liquids (Fig. 1) and used them in the
synthesis of dioctyl phthalate. The stability and reuse per-
formance of these FILs were examined and compared with
those of non-functionalized ionic liquids and the combina-
tion of neutral ionic liquids with Brønsted acid in order to
find a FIL which showed better catalytic activity and reuse
performance.

1566-7367/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2007.01.029
1760 H. Li et al. / Catalysis Communications 8 (2007) 1759–1762

F F O O 2.2.2. Preparation of 1-methyl-3-(3-sulfopropyl)-

N + N F B- F N + N - -
F B F O S OH
+ imidazolium hydrogen sulfate ([HSO3-pmim][HSO4])
F NH
F O

[emim] [BF4 ] I [b mim] [BF4 ] II [Hpyro] [HSO4 ] III

O- + N O
O N
N + N -O
O S OH
HO
S
O
N
+ N
-
O
O S OH O
S + HO S OH
O O
O O
[bmim] [HSO4] IV [H SO3-pmim] [HSO4] V
Δ O + N O
HO N -
O + N HO O O S O S OH
HO N O S -
S - + O S OH O
O O S O N O
O O
[HSO3-pmim] [pTSA] VI [H SO3-pPydin] [HSO4] VII

Fig. 1. Structures of ionic liquids prepared and used in this paper.
2. Experimental
2.1. Chemicals and instruments
1-Methylimidazole (MIM, 99%), 1,3-Propane sulfone
(1,3-PS, 99%) and other chemicals (AR) were commercially
available and used without further purification unless
otherwise stated.
NMR spectra were recorded on a BRUKER AV500
spectrometer in D2O and calibrated with tetramethylsilane
(TMS) as the internal reference. IR measurements were
performed on a Nicolet 510P FT-IR absorption spectrom-
eter using KBr or liquid film. The thermal properties were
examined by a NETZSCH STA-449C differential scanning
calorimetry-thermo gravimetric (DSC-TG) analyzer with a
scan rate of 10 °C per min in a dynamic N2 atmosphere.
Under vigorous stirring, MIM-PS was dissolved in
water and equal-mole sulfuric acid was dropped slowly at
room temperature. After the dropping was finished, the
system was slowly heated up to 90 °C and stirred for 2 h,
then the water was removed under vacuum (5–10 mm Hg)
at 90 °C, giving [HSO3-pmim][HSO4] as a light yellow vis-
cous liquid (yield 99%). 1H NMR (500 MHz, D2O) d 2.11
(m, 2H), 2.71 (t, 2H), 3.71 (s, 3H), 4.16 (t, 2H), 7.25 (s,
1H), 7.32 (s, 1H), 8.53 (s, 1H). IR(LF):m 3437, 3157,
2970, 1722, 1653, 1574, 1230, 1172, 1029, 853, 582.
2.2.3. Preparation of 1-methyl-3-(3-sulfopropyl)-
imidazolium 4-methylbenzenesulfonate ([HSO3-pmim]
[pTSA])

2.2. Preparation of functionalized ionic liquids

2.2.1. Preparation of 3-(1-methylimidazolium-3-yl)propane-

1-sulfonate (MIM-PS)

Equal-mole MIM-PS and 4-methyl benzenesulfonic acid

Under vigorous stirring, 1,3-propane sulfone was dis-
solved in toluene, equal-mole 1-methyl imidazole was
dropped slowly in a ice bath. After the dropping was fin-
ished, the mixture was slowly heated up to room tempera-
ture and stirred for 2 h, then the reaction mixture was
filtered to get the white precipitate. The precipitate was
washed with diethyl ether three times and dried at 100 °C
for 5 h, giving MIM-PS as a white powder (yield 95.6%).
1
H NMR (500 MHz, D2O): d 2.26 (m, 2H), 2.86 (t, 2H),
3.83 (s, 3 H), 4.30 (t, 2H), 7.38 (s, 1H), 7.46 (s, 1H), 8.70
(s, 1H). 13C NMR (125 MHz, D2O): d 24.79, 35.46,
46.97, 47.41, 121.85, 123.50, 135.82. IR(KBr): m 3450,
3154, 3110, 1640, 1575, 1195, 1043, 746, 622, 532.
were added in a mortar and be ground continuously, the
two white powders were slowly turned into achromic 1 vis-
cous liquid, [HSO3-pmim] [pTSA] (yield 100%). H NMR
(500 MHz, D2O) d 2.16(m, 2H), 2.24 (s, 3H), 2.78 (t,
2H), 3.72 (s, 3H), 4.18 (t, 2H), 7.20 (d, 1H), 7.26 (s, 1H),
7.35 (s, 1H), 7.54 (d, 2H), 8.56 (s, 1H). Other ionic liquids
(Fig. 1) used in this paper were synthesized according to the
literatures [5,7–10].
2.3. General procedure for synthesis of dioctyl phthalate
Weighed amounts of phthalic anhydride (PA), 2-ethyl
hexanol, ionic liquid, cyclohexane were added to a flask
with a reflux condenser, a water segregator and magnetic
stirring apparatus. The esterification reaction was typically
carried out for 2–12 h at the desired temperature with vig-
orous stirring. Then reaction mixture became biphasic, the
upper phase (volume VR), which was mainly desired dioctyl
 H. Li et al. / Catalysis Communications 8 (2007) 1759–1762 1761

phthalate, could be isolated simply by decantation; the
lower phase, viscous ionic liquid, could be reused without
any disposal. Conversion data were based on phthalic
anhydride through NaOH titration.
Conversion of PA was calculated using the following
formula:
 
CNaOH  VNaOH  VR
Conversion of PA ¼ 1   100%
NPA
3. Results and discussion
According to Table 1, using non-functionalized ionic
liquids as catalyst (Table 1 entries 3 and 4), the conversions
of PA were only a little higher than that of blank experi-
ment (Table 1 entry 1). Therefore, the non-functionalized
ionic liquids have weak catalytic activity. The catalytic
activity of the [bmim][BF4] (Table 1 entry 4) was better
than that of [emim][BF4] (Table 1 entry 3), this is probably
because the butyl on the ring of imidazole brings more lipo-
philicity [11] than the ethyl of the latter. This suggested that
more dispersibility of ionic liquid in the reaction fluid could
enhance its catalytic activity.
The catalytic activities of the combination of neutral
ionic liquids and Brønsted acid (Table 1 entries 5 and
6) were also examined. The conversion of PA was about
90% after reacting for 3 h, it is much better than those of
[bmim][BF4] and [emim][BF4], but still less than that of
H2SO4 (Table 1 entry 2). Compared with H2SO4, the con-
centration of Brønsted acid would become lower after dis-
solved in ionic liquids, so that the catalytic activities of
the combination of neutral ionic liquids and Brønsted
acid (Table 1 entries 5 and 6) was poorer than that of
H2SO4.
The ionic liquids which have H+ on its anions, [Hpyr-
o][HSO4] and [bmim] [HSO4] (Table 1 entries 7 and 8),
could dissolve gradually in the reaction fluids and could
not be separated with the products. Another two ionic
liquid [12], 1-methyl-imidazolium hydrogen sulfate and 1-
methyl-imidazolium fluorborate, were also examined and
give the same results. These ionic liquids might be decom-
posed under the reaction temperature and reaction fluid
surroundings. It is suggested that the structure of ionic
liquid has significant effect on the stability under the reac-
tion conditions.
The results showed that the catalytic activity of FIL was
better than those of the above-mentioned ionic liquids and
was nearly equivalent to that of H2SO4 (Table 1 entry 2).
However, the chrominance of product was much better
than that of using H2SO4 as catalyst.
[HSO3-pmim][HSO4] (Table 1 entry 9) has better con-
versions than that of [HSO3-pmim][pTSA] (Table 1 entry
10). We could attribute this result to the following two rea-
sons: firstly the acidity of HSO 4 is stronger than the
pTSA when the cation is same; secondly HSO 4 presents
the better immiscibility with the produced ester which facil-
itates the shifting of the esterification reaction equilibrium
to the product side. These were consistent with the results
of the literature [8].
The reuse performances of the FILs were showed in
Table 2. [HSO3-pmim][HSO4] (Table 2 entry 2) could be
reused for 8 times and the conversions of PA was not less
than 95%, and no obvious change in the property of ionic
liquid could be observed. On the contrary, the conversion
of PA decreased to 75% after [HSO3-pPydin][HSO4] was
reused for 6 times (Table 2 entry 1), and the ionic liquid
turned to white solid gradually. It was indicated that
[HSO3-pPydin][HSO4] was decomposed. Therefore, the

Table 1
Results of dioctyl phthalate synthesis using different ionic liquidsa
Entry Ionic liquids Dosageb (%w) T (°C) Time/h Conversionc (%)
1 Blank 0 115–125 12 32
2 H2SO4 2 115–125 1.5 98
3 [emim][BF4] I 15 115–125 12 36
4 [bmim][BF4] II 15 115–125 12 49
5 [bmim][BF4] + H2SO4 15 + 5 115–125 3 90
6 [bmim][BF4] + pTSA 15 + 5 115–125 3 89
7 [Hpyro][HSO4] III 15 115–125 1.5 Dissolved
8 [bmim][HSO4] IV 15 115–125 1.5 Dissolved
9 [HSO3-pmim][HSO4] V 15 115–125 1.5 98
10 [HSO3-pmim][pTSA] VI 15 115–125 1.5 86
11 [HSO3-pPydin][HSO4] VII 15 115–125 1.5 95
a
n(phthalic anhydride): n(2-ethyl-1-hexanol) = 1:2.5.
b
The dosage of the IL was weight percentage based on all reaction materials.
c
Conversion data were based on phthalic anhydride through NaOH titration.
1762 H. Li et al. / Catalysis Communications 8 (2007) 1759–1762

Table 2
The conversion of phthalic anhydride using reused ionic liquidsa
Entry Ionic liquidsb Conversion (%)
Cycle 1 2 3 4 5 6 7 8
1 [HSO3-pPydin][HSO4] 98 95 96 95 94 75
2 [HSO3-pmim][HSO4] 99 99 98 99 98 97 96 95
a
Reaction time 1.5 h; temp 115–125 °C; ionic liquids dosage 30%w.
b
Ionic liquids were simply reused without any further purification or dehydration.

Phthalic Anhydride
Dioctyl phthalate
2-Ethyl-1-Hexanol Dioctyl phthalate
Stirring Stop

Heating
Ionic Liquids
Ionic Liquids Ionic Liquids

Ionic Liquids to be recycled

Fig. 2. Scheme of reaction procedure.

main factor which affects the reuse performance of ionic Acknowledgements

liquid is its stability under the reaction temperature and
reaction fluid surroundings. This work was financially supported by the National Nat-
The DSC-TG data of [HSO3-pmim][HSO4] and [HSO3- ural Science Foundation of China (No. 30571463) and Nat-
pPydin][HSO4] indicated that the two ionic liquids were ural Science Foundation of Shandong (No. Y2005B07).
thermally stable when temperature was below 330 °C and
300 °C, respectively, for there no irreversible mass loss. References
This thermal stability is at least as good as those of pyrro-
lidinium mesylates and tosylates [13] and only 20 °C and [1] M. Yasunori, A. Masatomo. Jpn. Pat. JP278840, 2001.
50 °C blow than that of p1,xNfO salts [14]. And only a sin- [2] T.S. Throat, V.M. Yadav, G.D. Yadav, Appl. Catal. 90 (1992) 73.
[3] P. Alpana, C. Uma, Ind. J. Chem. Tech. 10 (2003) 44.
gle decomposition peak (DSC, 366.4 °C and 333.0 °C, [4] W.J. Swindall, Clean Techn. Environ. Policy 6 (2004) 149.
respectively), lose weight (81.57% and 86.47%, respec- [5] A.C. Cole, J.L. Jensen, I. Ntai, K.L.T. Tran, K.J. Weaver, D.C.
tively), indicated that the two ionic liquids were synthe- Forbes, J.H. Davis, J. Am. Chem. Soc. 124 (2002) 5962.
sized successfully and not simple admixture. These results [6] D.M. Li, F. Shi, J.J. Peng, S. Guo, Y.Q. Deng, J. Org. Chem. 69
could explain the reuse performance of the two ionic (2004) 3582.
[7] Y.Q. Cai, Y.Q. Peng, G.H. Song, Catal. Lett. 109 (2006) 61.
liquids. [8] H.B. Xing, T. Wang, Z.H. Zhou, Y.Y. Dai, Ind. Eng. Chem. Res. 44
In summary, the process of this reaction system could be (2005) 4147.
expressed as following schematic Fig. 2. [9] J.Z. Gui, X.H. Cong, D. Liu, X.T. Zhang, Z.D. Hu, Z.L. Sun, Catal.
Commun. 5 (2004) 473.
[10] G.Y. Zhao, T. Jiang, H.X. Gao, B.X. Han, J. Huang, D.H. Sun,
4. Conclusion Green Chem. 6 (2004) 75;
R. Laurie, S.B. Lionel, N.V.K.A. Sudhir, A.S. Mark, F.B. Joan,
For the synthesis of dioctyl phthalate, HSO3 – function- Green Chem. 7 (2005) 83.
alized Brønsted acidic ionic liquids show better catalytic [11] D. Urszula, P. Aneta, E. Frank, Green Chem. 8 (2006) 268.
[12] H.P. Zhu, F. Yang, J. Tang, M.Y. He, Green Chem. 5 (2003) 38.
and reuse performances than the non-functionalized ionic
[13] J. Golding, S. Forsyth, D.R. MacFarlane, M. Forsyth, G.B. Deacon,
liquids and the combination of neutral ionic liquids and Green Chem. 3 (2002) 223.
Brønsted acid. Therefore, an environmental friendly [14] A.F. Stewart, J.F. Kevin, C.H. Patrick, R.M. Douglas, F. Maria,
approach for the synthesis of dioctyl phthalate is provided. Green Chem. 8 (2006) 256.