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Int. j. eng. sci., Vol(4), No (6), June, 2015. pp.

69-73

TI Journals

International Journal of Engineering Sciences


www.tijournals.com

ISSN:
2306-6474
Copyright 2015. All rights reserved for TI Journals.

Novel Microwave Assisted Synthesis of Anionic Methyl Ester Sulfonate


Based on Renewable Source
Pawan D. Meshram *
Department of Oil Technology, University Institute of Chemical Technology, North Maharashtra University, Jalgaon -425 001 (Maharashtra), India.

Tushar D. Patil
Department of Oil Technology, University Institute of Chemical Technology, North Maharashtra University, Jalgaon -425 001 (Maharashtra), India.

Ghayas A. Usmani
Department of Oil Technology, University Institute of Chemical Technology, North Maharashtra University, Jalgaon -425 001 (Maharashtra), India.

Hansraj V. Patil
Department of Oil Technology, University Institute of Chemical Technology, North Maharashtra University, Jalgaon -425 001 (Maharashtra), India.

Namrata B. Pawar
Department of Oil Technology, University Institute of Chemical Technology, North Maharashtra University, Jalgaon -425 001 (Maharashtra), India.
*Corresponding author: pawan.dm@gmaill.com

Keywords

Abstract

Microwave synthesis
Palm oil
Anionic surfactant
CMC
Kraft Point

The trans-esterification of palm oil was carried out under microwave irradiation to prepare Palm oil methyl
ester (POME). The sulfonation of POME was carried out at refrigerated condition using chlorosulfonic acid
as a sulfonating agent. The resulting product after subsequent purification was neutralized with alkali to
yield anionic surfactant, methyl ester sodium sulfonate (MESS). The synthesized surfactant was
characterized by FTIR, 1H-NMR and 13C-NMR spectral techniques. The performance properties of
surfactant such as critical micelle concentration, kraft point, emulsifying power and foaming ability were
determined using standard methods.

1.

Introduction

Anionic surfactants are kind of important products for utilization in various industrial applications due to their excellent detergency performance
[1] and it accounts for more than 60 % of the total world production of surface active species [2]. Previously surfactants were been prepared
from the precursor materials of petroleum origin [3-6]. However, with rising petroleum prices and great concern towards environmental issues
have gained momentum to substitute the synthetic petroleum based surfactants with bio-compatible surfactants [7]. The plant oil based
oleochemicals have been used as intermediates to prepare the finished products such as anionic surfactants [8-10]. Among the several reported
anionic surfactants, the ester sulfonate derived from renewable oil source has attracted the researchers because of its suitability to replace the
conventional linear alkyl benzene sulfonates (LABS), an active constituent in detergent formulation [11,12]. The methyl ester sulfonate (MES)
as anionic surfactant offers better wetting and cleaning properties at low cost and is considered environment friendly due to its biodegradable
nature [13,14]. An extensive research has been published giving the methods of MES preparation and possible applications [8,13,15-20].
In present study, an effort is made to utilize Palm oil as renewable source for preparation of MES. The cold sulfonation of ester followed with
alkali neutralization was the designed pathway to obtain the product. Besides, the process optimization for fatty methyl ester synthesis was done
using microwave irradiation technique which reduced the reaction time and gave better yield. The prepared Palm oil based methyl ester sodium
sulfonate (MESS) was characterized using spectral techniques and standard methods.

2.

Experimental Procedure

2.1. Materials
Refined Palm oil was procured from local general store. The chemicals and reagents used in the study were of analytical grade, and were
purchased from Merck, Mumbai. The sulfonating agent, chlorosulfonic acid was obtained from Sisco Chem., Mumbai.
2.2. Microwave assisted synthesis of MESS
2.2.1 Preparation of methyl ester
The trans-esterification was performed with a stoichiometric amount of Palm oil (0.1851 mol) and solvent methanol (1.125 mol) along with
alkali catalyst (KOH, 1.0 wt. % of oil) placed in a 250 cc three necked round bottom flask equipped with motor stirrer. The whole assembly was
placed in a microwave digester unit (MAS-II, SINIO MODEL) with irradiation power set at 300 W. The reaction mixture was heated to 60 oC
under microwave irradiation to enhance the rate of reaction. The reaction was stopped after 10 min of irradiation and the completion of transesterification reaction was confirmed by formation of methyl ester (ME) as determined using TLC technique. Two layer of mixture formed
thereof was separated by gravity separation to obtained the methyl ester and glycerol. The methyl ester separated was washed with deionized
water till stable pH near to neutral was achieved and further subjected to vacuum distillation for elimination of any residual moisture from the
ester product. The liquid ester was clear with light amber color and was comparatively less viscous from the precursor Palm oil.

Pawan Devidas Meshram *, Tushar D Patil, Ghayas A Usmani, Hansraj V Patil, Namrata B Pawar

70

International Journal of Engineering Sciences Vol(4), No (6), June, 2015.

CH2-OH

CH2-COOR1
KOH
R2OOC-HC

3 CH3-OH

CH2-COOR3
Triglycerides

Microwave Irradiation- 300 W


at 60 0C , 10 min

Methanol

3R-CH2-COOCH3

+ CH-OH
CH2-OH

Methyl Ester

Glycerol

R= C16H34 (Palmitic)

Scheme 1. Preparation of methyl ester


2.2.2 Cold sulfonation of methyl ester
The above synthesized ME (0.1925 mol) was placed in a 250 cc three necked round bottom flask equipped with motor stirrer, a thermometer and
a suction pipe. The flask was immersed in a refrigerated circulation water bath able to maintain the temperature near to 0 oC. The excess of
chlorosulfonic acid (0.294 mol) added drop wise to the ME under constant agitation at 0 oC for about 2 hours. The acidic fumes generated during
the reaction were sucked out by vacuum application and neutralized in alkaline solution. The decline in fume generation was taken as indicative
of completion of sulfonation. The unreacted chlorosulfonic acid was removed by water washing of the sulfonated product. Chemical bleaching
of the sulfonated mass was done by refluxing it with known amount of solvent ethanol and 2 gm of hydrogen peroxide for 30 min. The lighter
phase of solvent impured with hydrogen peroxide was separated through centrifuge and the bleached sulfonated product was obtained. This
bleached mass was then again dispersed in fresh solvent ethanol and neutralize with 20 % NaOH solution to the phenolphthalein indicator end
point to yield a precipitate of methyl ester sodium sulfonate (MESS). The product was dried under vacuums to obtain fairly yellow colored
powder (yield 73 %).
R-CH2-COOCH3
Methyl Ester

+ ClSO3H
Chlorosulfonic
Acid

0 oC, 4 hrs

R-CH-COOCH3

HCl

ClSO3H
Methyl ester
sodium sulfonate

Scheme 2. Synthesis of methyl ester sodium sulfonate


2.3. Characterization of MESS
The IR spectrum of the synthesized surfactant, MESS was recorded by SHIMADZU FTIR-8400 in the 400-4000 cm-1 range using KBr pellets.
1
H-NMR and 13CNMR spectra were recorded with Bruker advanced 400 MHz NMR spectrophotometer. The surface morphology of the MESS
powder was analyzed using field emission scanning electron microscope (FESEM) S 4800 type-II (Hitachi, Japan).
2.4. Determination of performance properties of MESS
Surface tension and critical micelle concentration - Surface tensions of different concentrations of aqueous solutions of MESS were measured
using Du Nouy Tensiometer model no. 63 according to ASTM D1331-56 method. The critical micelle concentration (CMC) was approximated
from the plot of surface tension vs. logarithmic concentration.
Conductimetry measurements - Kraft point of synthesized surfactant was determined by conductivity measurement using HM-Digital
conductivity meter (EC-Range 0.9999 s) according to method reported elsewhere [21]. The 0.1 wt. % solution of MESS was prepared and
placed in the incubator shaker maintained at 5 oC. The conductivity of the surfactant solution was then measured with increasing temperature in
a step of 2 oC up to 55 oC. Kraft temperature is given by the slope break in the conductivity verses temperature curve. This temperature is the
same as that required to completely dissolve the solid surfactant.
Wetting Power- Wetting property of MESS was evaluated by Draves test at 25 oC using 5 gm cotton skein. In this test, the wetting rates were
determined at three MESS concentrations of 0.1, 0.2 and 0.3 g/100 ml.
Emulsifying power - Emulsifying power of the aqueous solutions of MESS was determined for water/liquid paraffin (light) system by measuring
the time of separation of aqueous phase from the emulsion [22].
Foaming ability - The foaming property of aqueous solutions of the MESS product was determined using standard Rose-Miles method at
different concentration of the surfactants.

3.

Results and Discussion

3.1. Spectroscopic Characterization


3.1.1 FTIR
The infrared spectrum of the MESS is shown in Fig. 1. The peaks appearing at 2923 cm-1 and 2853 cm-1 are attributed to the symmetric and
asymmetric CH2 stretching. The characteristic absorption band at 1741 cm-1 and 1466 cm-1 can be assigned to stretching vibration of C=O and
CH2 bending respectively. Another peak at 1298 cm-1 represents the C-O group functionality. The presence of sulfonate group (-C-S=O) in the
surfactant structure is credited to the typical absorption bands at 1093 cm-1 and 776 cm-1 .
3.1.2 1H-NMR
The 1H-NMR spectra of MESS is shown in Fig. 2. The details of the characteristics peaks appearing the spectra is as follows: (400 MHz,
DMSO): 0.89 (3H, t, JCH2-CH3), 1.25-1.27 (22H, m, 11CH2), 2.2-2.5 (2H, m, JCH3 -CH2, CH2), 1.38-1.58 (2H, m, JCH-CH2, CH 2), 3.60 (1H,
d, JCH 2-CH, CH), 3.68 (3H, s, CH 3).
3.1.3 13C-NMR
The 13C-NMR spectra of MESS as shown in Fig. 3 revealed the characteristics peaks discussed as follows: (400 MHz, DMSO): 13.63 (CH 3),
24.31-24.38-28.45-28.55-28.61-28.68-28.79-28.85-28.91-29.09-29.77-31.55 (12 CH 2), 50.1 (CH 3), 38.8-40.1 (CH2), 173-175 (C=O).

71

Novel Microwave Assisted Synthesis of Anionic Methyl Ester Sulfonate Based on Renewable Source
International Journal of Engineering Sciences Vol(4), No (6), June, 2015.

Figure 1. FTIR spectra of synthesized MESS

Figure 2. 1 H-NMR Spectra of synthesized MESS

Figure 3. 13C-NMR Spectra of synthesized MESS

Pawan Devidas Meshram *, Tushar D Patil, Ghayas A Usmani, Hansraj V Patil, Namrata B Pawar

72

International Journal of Engineering Sciences Vol(4), No (6), June, 2015.

3.2. Surface Morphology


As seen in Fig. 4 the surface morphology of MESS showed folded plates structures overlapped on each other to form a thick layered mass. In
addition, some rod shaped extrudes were also observed.

Figure 4. Scanning Electron Micrographs of MESS


3.3. Surface Activity
The surface tension of water (72 dynes/cm at 25 oC) is normally reduced to a value 30-40 dynes/cm at the CMC of surfactant. The variation in
the surface tension values versus log concentration for MESS solutions at 25 oC is represented in Fig. 5. The surface tension reduced drastically
as the concentration of MESS in aqueous solution increased. However, at a point of particular concentration the surface tension approached to
stability and showed no further reduction of surface tension values. This point was recorded as to show the concentration of MESS in aqueous
solution that represent the CMC value of MESS (0.0005 mol/L) corresponding to the surface tension value of 32.6 dynes/cm.
3.4. Kraft Temperature
The temperature at which the solubility becomes equal to the critical micelle concentration (CMC) called as Kraft temperature. It was
determined by measuring the conductance as function of varying temperature (Fig. 6). Kraft temperature of the synthesized MESS was obtained
as 35 oC which represent the temperature of complete solubility for MESS surfactant in aqueous media.

Figure 5. Equilibrium surface tension curve of MESS

Figure 6. Conductance - temperature plot of MESS at 0.1 mol/L solution

3.5. Emulsifying power


Emulsifying power (EP) of the aqueous solutions of MESS was determined for water/liquid paraffin (light) system using different concentration
of MESS (Table-1). In general, EP increases with increased amount of surfactant in the immiscible binary mixture. The more is the time
requiring clearing the two layers, the higher is the emulsifying power of the surfactant. The addition of 0.01g/L of MESS solution in equal
volume proportion to the liquid paraffin was found to be ineffective for emulsification since the separation of two phases occurred
instantaneously. Besides, further increasing the concentration of MESS solution showed relative emulsification power. At steady storage
conditions, it was observed that the emulsion stability gradually decreased as time passed. This may be due to breaking of dispersed droplets
within the system and subsequent segregation of two phases [22]. When using higher concentration of MESS (0.05 g/L), a stable creamy
emulsion was obtained which took about 38 min to effect separation.
3.6. Foaming power and stability
The most widely appreciated property of the surface active substances in aqueous solution is their ability to encourage the formation of foam and
bubbles. These behaviors could be endorsed to the physical nature and bubble development [23]. In present case, the concentration of MESS was
varied to investigate the effect on the foaming ability. The results obtained for MESS showed that at lower concentration (0.01 g/L) depth of
foam formed was least with full of larger bubbles and thus, the foam diminished almost for the given period of observation period. The
increasing MESS concentration enhanced the dense foam production with increased depth. At higher concentration (0.05 g/L) of MESS, very
thick high quality foam was observed indicating the dispersion air in the form of small bubbles throughout the solution blend. Besides, a stable
foam volume was obtained showing the stability of the MESS foam at that concentration for the experimental period.

73

Novel Microwave Assisted Synthesis of Anionic Methyl Ester Sulfonate Based on Renewable Source
International Journal of Engineering Sciences Vol(4), No (6), June, 2015.

3.7. Wetting Power


The Draves test was performed to evaluate the wetting power of MESS surfactant at different concentration levels. Since the time of wetting is a
function of the surface tension of the wetting front, the wetting power of a surfactant is a function of the concentration of molecularly isolated
substance at the front [24]. The addition of increased concentration of MESS in solution was found to reduce the wetting time of the cotton
skein. The mechanism of wetting may involve the reduction of surface tension by surfactant moiety in the aqueous solution, thereby promoting
the better contact at solid-liquid interface. Thus, the higher concentration (0.05 g/L) of MESS showed faster wetting of cotton skein indicating its
suitability for possible application as wetting agent.
Table 1. Emulsifying power, wetting time and foam stability of MESS at different concentration.

4.

MESS Conc.
(g/L)

EP
(min)

Wetting time
(sec)

Initial Foam volume


(ml)

Foam volume
(ml) at 300 sec

0.01

19

48

0.02

16

125

85

0.03

12

14

161

123

0.05

38

468

196

Conclusion

The renewable source, Palm oil was successfully utilized for preparation of methyl ester sodium sulfonate (MESS). A novel microwave assisted
reaction mechanism was established to reduce the production time and to obtain high yield of product. The synthesis of the ester sulfonate was
confirmed using FTIR and NMR spectral techniques. The synthesized ester sulfonate as an anionic surfactant showed fairly low CMC value
(0.0005 mol/L) corresponding to the surface tension value of 32.6 dynes/cm, and Kraft point was noted to be 35 oC. The SEM micrographs
illustrated the plate and rod shape like structures of the ester sulfonate. The results for various performance tests were obtained using standard
methods which showed suitability of the prepared ester sulfonate as effective wetting, foaming and emulsifying agent. Thus, the ester sulfonate
can find its place in various chemical industries such paint, polymer, textile and particularly in detergents for its active properties.

Acknowledgements
The authors are very much thankful to the TEQIP-II, funded by MHRD, Government of India, Delhi (India) for providing financial support to
carry out this work. Authors also acknowledge the support extended by SAIF, Punjab University, Chandigarh for sample characterization.

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