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ENVIRONMENTALLY BENIGN ENCAPSULATED FUNCTIONAL IONIC LIQUIDS AS

CATALYSTS FOR SYNTHESIS OF PHENOLIC COMPOUND BASED ANTIOXIDANT

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American International Journal of Available online at http://www.iasir.net
Research in Science, Technology,
Engineering & Mathematics
ISSN (Print): 2328-3491, ISSN (Online): 2328-3580, ISSN (CD-ROM): 2328-3629
AIJRSTEM is a refereed, indexed, peer-reviewed, multidisciplinary and open access journal published by
International Association of Scientific Innovation and Research (IASIR), USA
(An Association Unifying the Sciences, Engineering, and Applied Research)

ENVIRONMENTALLY BENIGN ENCAPSULATED FUNCTIONAL

IONIC LIQUIDS AS CATALYSTS FOR SYNTHESIS OF PHENOLIC
COMPOUND BASED ANTIOXIDANT
Pandian Elavarasan1*, Sreedevi Upadhyayula2
1
Department of Chemical Engineering, Annamalai University
Annamalai nagar, Tamil Nadu- 608002, INDIA
2
Department of Chemical Engineering, Indian Institute of Technology Delhi,
HauzKhas, New Delhi -110016, INDIA
arasu2@gmail.com pe08135@annamalaiuniversity.ac.in

Abstract: Present investigation is production of tert-butyl cresol (TBC) by reaction of tert-butylation with
cresol using encapsulated functional ionic liquid. Ionic liquids have recently emerged as promising, benign
and recoverable catalysts for many organic reactions. However, there are still a few problems in their use
which come in the way of their commercialization. These problems are, escalated costs due to the need for
high purification, hygroscopicity, their requirement in large quantities. This work was undertaken to
overcome these problems. Highly dispersed ionic liquid catalysts were prepared through physical
confinement or encapsulation of ionic liquids in a silica-gel matrix through a sol gel process. Three ionic
liquids, namely, (N-(4-sulfonic acid) butyl triethylammonium hydrogen sulfate), (1-(4-sulfonic acid)
butylpyridinium hydrogen sulfate) and (1-(4-sulfonic acid) butyl-3-methylimidazolium hydrogen sulfate)
were used to prepare the silica gel encapsulated catalysts. The loading of ionic liquids in silica gel was 5 -
30 % by weight. They were characterized by NMR, XRD, FTIR and SEM. Thermogravimetric analysis was
carried out under inert. The analysis showed that they were thermally stable upto 324ºC. The catalysts were
tested foractivity in production of antioxidant TBC in a batch reactor. The conversion of p-cresol was 80%
using all the three encapsulated ionic liquids at a temperature of 70ºC with a maximum selective of TBC
yield of 87% is achieved.

Keywords: Antioxidant, TBC, Ionic liquids, encapsulation

I. Introduction
Alkylation of cresol with tert-butanol is most important industrial reaction for antioxidant production [1]. Ionic
liquids (ILs) are generally defined as salts melting at or below 100°C. The liquid salts are basically composed of
relatively large organic cations and inorganic or organic anions. Any change of the structure or of the length of
the carbon side chain of both ions leads to different chemical or physical properties. They have a negligible
vapour pressure and are generally assumed to be stable over a wide temperature range. Depending on the
application, ionic liquids can be designed to meet the demands. Numerous of these ionic phases have been
examined in a variety of different areas reaching from material synthesis to separation science for alternative
reaction media. Particularly, ionic liquids are used as catalyst for many of the reaction in homogeneous or
heterogeneous reaction at room temperature. These catalysts produce the high selective yield, conversion and
recyclable, even though the separation of ionic liquids requires more amount of organic solvent as well as the cost
of ILs is high [2-6]. An alternative approach has recently been established which is immobilization of the ionic
liquids using solid support [6]. The immobilization ionic liquids show similar or improved chemical behaviors
and have simplified separation process being a solid. Sulfonic acid functional ionic liquids have been reported for
esterification and alkylation reaction with high conversion with selective product yield. In particular, alkylation of
cresol was performed with function ionic liquids. Present study, immobilization of the functional ionic liquids
have been sol-gel method have been reported. Highly dispersed ionic liquid catalysts were prepared through
physical confinement or encapsulation of ionic liquids in a silica-gel matrix through a sol gel process. Activity of
encapsulated ionic liquids is test with alkylation of p-cresol with tert-butanol[1-8].
II. Materials and methods
Sulfonic acid functional bronsted acidic ionic liquids were prepared in the laboratory following procedure have
been adopted [3-5]. Triethylamine was mixed with 1,4-butane sultone by stirring at 40-80°C for an 12-24 hours.
After solidification, the produced zwitterions mass was washed three times using ethyl ether and dried under
vacuum (120°C and 0.01 torr). Stoichemetric amount of sulfuric acid is added to the zwitterions and the mixture
was stirred at 80°C for 8 hours to obtain ionic liquid. The structures of the ionic liquids are presented in figure 1.

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 Elavarasan et al., American International Journal of Research in Science, Technology, Engineering & Mathematics, Special issue of
National Conference on Innovations in Bio, Chemical and Food Technology (IBCFT -2019), February 02, 2019, pp. 09-12

Figure 1 Structure of Ionic Liquids

A mixture of tetraethoxyorthosilicate (TEOS, 10 ml) and ethanol (7 ml) was heated to 60 0C and the ionic
liquids (ILs) (2 to 4 g) were immediately transferred into the TEOS. After the formation of a clear and
homogeneous liquid mixture, hydrochloric acid (5 M, 5ml) was added and the mixture gradually coagulated [7].
After aging at 60°C for 12 hours, the resulting solid material was dried in vacuum at 150 °C for 3 h and 3-7 g of
solid sample was obtained. A dry solid sample of silica-gel-confined ionic liquid (loading of up to 55% and 40%
based on original weight) was obtained, indicating that the ionic liquid added could be completely encapsulated
into silica gel. The alkylation experiments were carried out in sealed glass tube with autogeneous pressure at
given temperature. A typical batch is containing 10 mmol each of p-cresol, tert-butyl alcohol and 2 g
encapsulated ionic liquids. Reaction temperature was maintained at 70°C and reaction mixture was stirred around
800 rpm for an 8 hours. At the end of reaction, the mixture was cooled and the products were extracted by
toluene. A qualitative product analysis was conducted with using a GC-MS and quantitative analyses were
conducted by using NUCON GC which is supplied by AIMIL India Ltd using a CHROMSORB-WHP (2 m x
3.175 mm x 2 mm) column and flame ionization detector.
III. Results & Discussion
The decomposition temperature of ionic liquid and encapsulated ionic liquid, the decomposition temperature are
same in both cases and only ionic liquid has been decomposed at particular (325 C) temperature was observed
thermo gravimetric analysis. FT-IR spectra of IL1 (a) shown in the figure 2. From the IR spectra the silica gel and
encapsulated ionic liquid shows the similar peak. XRD of the silica gel and immobilized IL shows amorphous
nature. Figure 4 shows the SEM image of silica gel (a) and encapsulated IL (b & c). Average size of silica gel
particles is - s are
entrapped with the silica gel particles.

Figure 2 FT-IR spectra for IL1 (a), pure silica gel (b) and encapsulated ionic liquid (c)

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 Elavarasan et al., American International Journal of Research in Science, Technology, Engineering & Mathematics, Special issue of
National Conference on Innovations in Bio, Chemical and Food Technology (IBCFT -2019), February 02, 2019, pp. 09-12

The influence of reaction time on conversion of p-cresol and the selectivity towards TBC & DTBC was studied at
different temperatures and different reactant mole ratios. Table 1 shows the conversion of p-cresol at 70°C, 1:1
molar ratio of p-cresol / TBA and 1:1 catalyst to reactant ratio. The alkylation of p-cresol with TBA in the
supported IL1 gave a mixture of TBC, 2, 6-di-tert-butyl-3-methyl phenol (2,6-DTBC) and negligible amount (<
0.2%) of tert-butyl-p-cresol ether (TBCE). With increase in reaction time, the conversion of p-cresol and
selectivity to TBC and the yield of TBC increased rapidly and reached maximum after 24 h from figure 4. The
conversion of p-cresol reached 68.4%, the selectivities to TBC and DTBC reached to 76.2% and 22.4%
respectively after 24 h. The increase in the selectivity to DTBC led to decrease in selectivity to TBC with time but
the combined selectivities of TBC & DTBC almost remains constant over the time period.

Figure 3 SEM images for pure silica gel (a), encapsulated IL1 (b) and surface of the encapsulated IL1 (c)

Table 1 Activity of encapsulated IL in alkylation of p-cresol with tert-butyl alcohol

Conversion of p- Selectivity of 2,
Catalyst Selectivity of 2-TBC
cresol 4-DTBC
IL1 64.5 72.3 25.4
IL2 63.6 76.4 22.5
IL3 63.4 74.8 24.7

Figure 3 Effect of reaction time Figure 4 Effect of reaction temperature

Figure 5 Effect of different IL loading on sol-gel

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Elavarasan et al., American International Journal of Research in Science, Technology, Engineering & Mathematics, Special issue of
National Conference on Innovations in Bio, Chemical and Food Technology (IBCFT -2019), February 02, 2019, pp. 09-12

The reaction was studied at various temperatures from 50°C to 90°C. Figure 5 shows the variation of p-cresol
conversion and selectivity to different products with temperature. At 50° C the conversion of p-cresol is 34.4 %
and increased to 69.7 % at 90°Cand 1:1 molar ratio of p-cresol / TBA and 1:1 catalyst to reactant ratio. The
selectivity to DTBC is high (14 %) at 50°C and as the temperature is increased, the selectivity to DTBC
increased. The highest selectivity to DTBC was found to be 24 % due to higher stability and the availability of
solvated tert-butyl cation at reaction temperatures. The effect of different loading of IL on supported catalyst on
p-cresol conversion, TBC and DTBC selectivities were investigated using supported ionic liquid from 2 to 4.8 g
at 70°C and TBA / p -cresol molar ratio constant at 1:1, which can be shown in Figure 7. As loading IL is
increased, the p-cresol conversion and DTBC selectivity increased to maximum. Highest conversion of p-cresol
and highest selectivity of TBC was achieved without any unwanted product, when IL / p-cresol molar ratio
maintained at 1:1. Using higher amount IL in the reaction led to leaching.
IV. Conclusion
Highly dispersed ionic liquid catalysts were prepared through physical confinement or encapsulation of ionic
liquids in a silica-gel matrix through a sol gel process for production of antioxidant. Three ionic liquids, namely,
(N-(4-sulfonic acid) butyl triethylammonium hydrogen sulfate), (1-(4-sulfonic acid) butylpyridinium hydrogen
sulfate) and (1-(4-sulfonic acid) butyl-3-methylimidazolium hydrogen sulfate) were used to prepare the silica gel
encapsulated catalysts. The loading of ionic liquids in silica gel was 5 - 30 % by weight. They were characterized
by NMR, XRD, FTIR and SEM. Thermogravimetric analysis was carried out under inert atmosphere on all the
encapsulated ionic liquids in order to determine their exact thermal degradation or decomposition temperature as
well as water and other organic impurities. The analysis showed that they were thermally stable upto 324ºC. The
catalysts were tested for activity in tert- butylation of p-cresol with tert-butyl alcohol (TBA) in a batch reactor.
The maximum conversion of p-cresol was 80% at a temperature of 70ºC using all the three encapsulated ionic
liquids with a maximum selective yield of 87% monoalkylated product which is TBC.
V. References
[1] P. Elavarasan, K. Kondamudi, S. Upadhyayula, "Synthesis of Antioxidants : Green Chemistry Route," International Journal of
Chemical Sciences, Vol S579 (1), Dec 2010, pp. 579-582.
[2] -temperature ionic liquids. Solvents for synthesis and catalysis," Chemical Review, vol. 99(8), July 1999, pp
2071 2084, DOI: 10.1021/cr980032t.
[3] P. Elavarasan, K. Kondamudi, S. Upadhyayula, "Statistical optimization of process variables in batch alkylation of p-cresol with
tert-butyl alcohol using ionic liquid catalyst by response surface methodology.", Chemical Engineering Journal, Vol 155 (1-2),
Jan 2009, pp. 355-360. Doi:10.1016/j.cej.2009.07.019.
[4] K. Kondamudi, P. Elavarasan, P. J. Dyson and S. Upadhyayula, "Alkylation of p-cresol with tert-butyl alcohol using benign
Bronsted acidic ionic liquid catalyst.", Journal of Molecular Catalysis A: Chemical, Vol 321(1-2), Apr 2010, pp. 34-41. Doi:
10.1016/j.molcata.2010.01.016.
[5] P. Elavarasan, K. Kondamudi and S. Upadhyayula, "Kinetics of phenol alkylation with tert-butyl alcohol using sulfonic acid
functional ionic liquid catalysts.", Chemical Engineering Journal, Vol 166 (1), Jan 2011, pp. 340-347. Doi:
10.1016/j.cej.2010.11.001.
[6] P. Elavarasan, K. Kondamudi and S. Upadhyayula, "A Functionalized, Supported Ionic Liquid for Alkylation of p-Cresol with
Tert-Butyl Alcohol.", Journal of Chemical Engineering & Process Technology, Vol 7 (1), Jan 2016, pp. 1-7. Doi: 10.4172/2157-
7048.1000270..
[7] -6. DOI: 10.1002/chem.200400683
[8] --a new concept for
-12933.
doi/10.1021/ja0279242

VI. Acknowledgments
This research was supported by QIP-AICTE PhD program at Indian Institute of Delhi, New Delhi, India.

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