INTERNATIONAL JOURNAL OF ADVANCED RESEARCH IN ENGINEERING AND TECHNOLOGY (IJARET)

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1 INTERNATIONAL JOURNAL OF ADVANCED RESEARCH IN ENGINEERING AND TECHNOLOGY (IJARET) International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 ISSN (Print) ISSN (Online) Volume 5, Issue 8, August (2014), pp IAEME: Journal Impact Factor (2014): (Calculated by GISI) IJARET I A E M E SYNTHESIS, CHARACTERIZATION AND PERFORMANCE PROPERTIES OF GLYCEROL BASED NON-IONIC GEMINI SURFACTANT WITH 1, 6-DIBROMOHEXANE AS SPACER ISHWAR T. GAWALI*, GHAYAS. A. USMANI Department of Oil Technology, University Institute of Chemical Technology, North Maharashtra University, Jalgaon , MS, India ABSTRACT The synthesis of novel glycerol based non-ionic Gemini surfactant was carried out in two stages in the present research work. Initially glycerol was esterified using cotton seed oil at higher temperature followed by reaction with 1, 6-dibromohexane to form the Gemini surfactant. The new Gemini surfactant was characterized by FTIR, 1 H-NMR and 13 C-NMR spectroscopy. The surfactant properties such as surface tension, critical micelle concentration, effectiveness, foaming power and stability, emulsifying power, wetting power, dispersion capability, contact angle and solubilization behaviour were studied. Keywords: Gemini Surfactant, Characterization, Surface Activities, Performance Properties, Contact Angle Measurement, Solubilization Behaviour. 1. INTRODUCTION Surfactants are amphiphilic molecules that are capable of undergoing self-assembly into aggregated system. These unique molecules generally consist of a polar head group and one or more hydrophobic tails. As a consequence of the hydrophobic effect, the surfactants within the aggregated assemblies are oriented with their polar head groups to the aqueous phase and their hydrophobic tail away from the aqueous phase. Gemini surfactants are a newer type of surfactants capable of forming self assemblies having two amphiphiles in molecules, chemically bonded through a spacer group. They are more surface active by order of magnitude than conventional surfactants. They have good water solubility and their ability to form micelles and lowering surface tension characteristics are fairly good as compared to conventional surfactants. This newer type of surfactants has attracted considerable interest since it became evident that these compounds have a very low critical micelles 62

2 concentration and much greater efficiency in reducing surface tension than expected [S. K. Hait et al, 2013, R. Janardhan et al, 2012, Wenjian Zhang et al, 2009]. There are several research publications on Gemini surfactants and their potential applications. Aratani et al have synthesized Gemini surfactants from tartaric acid and studied properties. Anno Wagennaar et al was synthesized non-ionic reduced-sugar based bola amphiphiles and gemini surfactants with an α, ω-diamino-(oxa) alkyl spacer. Wenjian Zhang et al synthesized Nonionic Gemini Surfactant Di-Glycerol 2, 9-Dihexyldecanedioate and studied the physico-chemical properties. In the present research work, a new Gemini surfactant using glycerol as hydrophilic head group and cotton seed oil as source of hydrophobic tail has been synthesized. There is industrial important for the use of glycerol due to its low cost factor. Cotton seed oil contains linoleic acid as a major component. Pure linoleic acid is not cost effective and may not be economic for the industrial use. Synthesis involved initial trans-esterification of cotton seed oil with glycerol to form monoglyceride which was then dimerised using 1, 6-dibromohexane. The prepared non-ionic Gemini surfactant was characterized and surfactant properties were investigated in detail. 2. EXPERIMENTAL PROCEDURES 2.1 Materials and Equipment Setup- The cotton seed oil was procured from local market. Glycerol with purity > 99%, Calcium oxide, 1, 6-dibromohexane, Tetra-butyl ammonium bromide, Potassium hydroxide were purchased from Merck. An infrared (IR) spectrum was obtained by SHIMADZU FTIR 8400 in the cm -1 range using KBr pellets. 1 H nuclear magnetic resonance ( 1 H NMR) spectra were obtained with Bruker advanced 400 MHz NMR spectrophotometer. 13 C nuclear magnetic resonance ( 13 C NMR) spectra were obtained with Bruker advanced 400 MHz NMR spectrophotometer. 2.2 Experimental section: Step 1- Synthesis of glycerol Ester from Cotton seed oil and Glycerol by trnas-esterification reaction. The experimental set up consisted of a 250 ml three necked round bottom flask equipped with motor stirrer, a thermometer and condenser. The cotton seed oil (90 gm, 0.1 moles) was reacted with glycerol (23gm, 0.25 moles) by using calcium oxide (1% of total amount of oil) as catalyst. Firstly, the catalyst was dispersed in the oil. Then reaction mixture was heated to 80 O C for half an hour and temperature was increased to O C. The reaction was continued for three hours in the inert atmosphere under the presence of nitrogen. The oil bath was used to maintain the constant temperature. The formation of glycerol ester was analyzed by using solubility test in methanol [Wim D. Bossaert et al, 1999]. Scheme-1 Synthesis of Glycerol ester from cotton seed oil Step 2: Synthesis of gemini surfactant by using 1, 6 dibromohexane as spacer Glycerol ester 0.1 mole (31.2 gm), KOH 90 ml (20%) and Tetra butyl ammonium bromide (1 gm) were successively introduced in a 500 ml three necked round bottom flask and stirred vigorously for 15 minute at 25 O C. 1,6-dibromohexane was then added drop wise (12.1gm). At the 63

3 end of addition, temperature was raised to 100 O C and mixture was stirred vigorously for 24 hours. The organic phase was then separated, dried over sodium sulfate. The product was filtered under reduced pressure [Sebastien Queste et al, 2006]. Scheme-2 Synthesis of non-ionic Gemini surfactant from glycerol ester and 1, 6 - Dibromohexane. 3. RESULTS AND DISCUSSION 3.1 Characterization FTIR- IR spectra of Gemini surfactant is given in fig. 1. It shows absorption band at 1734 cm -1 (C=O stretching), 2928 cm -1 and 2857 cm -1 (C-H asymmetric and symmetric stretching in methylene and methyl group), 1459cm -1 (C-H bending streching), cm -1 (C-O stretching in C-O of ether), 3414 cm -1 (OH- symmetric stretching), 715 cm -1 for -(CH 2 )n- skeletal present in synthesized compound [B. S. Furniss et al, 1989] %T Fig. 1: FTIR spectra of synthesized Non-ionic Gemini Surfactant 500 1/cm H-NMR- The 1 H-NMR spectra of Gemini surfactant assigned for observed peaks is shown in fig. 2. The shift at 0.9 ppm and 1.3 ppm are due to the presence of methyl (CH 3 ) and methylene (CH 2 ) group in synthesized compound respectively. The multiplet accruing at 3.7 ppm to 3.4 ppm may be due to the ether group i.e. CH 2 -O-C group present in the synthesized compound. The proton with δ-value at 1.5 ppm is due to the CH- proton present in the compound. The proton with δ-value at 5.5 ppm is due to the proton attached to oxygen atom i.e. presence of the hydroxyl group (OH) in the synthesized compound. The δ-value at 2.1 ppm is due to the ester group i.e. CH-CO-OR [B. S. Furniss et al (1989)]. Some extra peaks were obtained. They resulted not only from the synthesized compound but also from the other byproduct and unreacted compounds. 64

4 GSB BRUKER AVANCE II 400 NMR Spectrometer SAIF Panjab University Chandigarh Current Data Parameters NAME Nov EXPNO 320 PROCNO 1 F2 - Acquisition Parameters Date_ Time 6.05 INSTRUM spect PROBHD 5 mm PABBO BB- PULPROG zg30 TD SOLVENT D2O NS 16 DS 2 SWH Hz FIDRES Hz AQ sec RG 45.2 DW usec DE 6.00 usec TE K D sec TD0 1 ======== CHANNEL f1 ======== NUC1 1H P usec PL db SFO MHz F2 - Processing parameters SI SF MHz WDW EM SSB 0 LB 0.30 Hz GB 0 PC ppm avtar_saifpu@yahoo.co.in Fig. 2: 1 H-NMR spectra of synthesized Non-ionic Gemini Surfactant C-NMR- The 13 C-NMR spectra of Gemini surfactant obtained for the observed peaks is shown in fig.3. The chemical shift at 182 ppm may be assigned to the C=O of ester. The various peaks at ppm are due to the presence of methyl and methylene group in synthesized compound. The chemical shift at 62 ppm may be assigned to the RCH 2 OR i.e. ether group present in the compound. The peak accruing at 72 ppm is due to the presence of CH-OH moiety in the compound. The presence of unsaturated alkyl chains are evident from the line at ppm [L. M. Harwood et al, 2011]. GSB BRUKER AVANCE II 400 NMR Spectrometer SAIF Panjab University Chandigarh Current Data Parameters NAME Nov EXPNO 322 PROCNO 1 F2 - Acquisition Parameters Date_ Time 6.38 INSTRUM spect PROBHD 5 mm PABBO BB- PULPROG zgpg30 TD SOLVENT D2O NS 512 DS 4 SWH Hz FIDRES Hz AQ sec RG 2050 DW usec DE 6.00 usec TE K D sec d sec DELTA sec TD0 1 ======== CHANNEL f1 ======== NUC1 13C P usec PL db SFO MHz ======== CHANNEL f2 ======== CPDPRG2 waltz16 NUC2 1H PCPD usec PL db PL db PL db SFO MHz F2 - Processing parameters SI SF MHz WDW EM 0 SSB LB 1.00 Hz 0 GB PC ppm avtar_saifpu@yahoo.co.in Fig. 3: 13 C-NMR spectra of synthesized Non-ionic Gemini Surfactant 3.2 Physicochemical Properties Surface Activity-Surfactant form aggregates of molecules called micelles, which are formed when the concentration of surfactant solute in the bulk of the solution exceed a limiting value, called critical micelle concentration (CMC), which is the fundamental characteristic of each solute-solvent system. If the interfacial property of a surfactant solution is plotted as a function of the concentration of the solution, the interfacial properties is vary linearly with the concentration up to the CMC, at which point there is a break in the curve as shown in Fig. 4. The surface tension of water (72 mn/m at 25 O C) is normally reduced to a value mn/m at the cmc of surfactant. Gemini surfactant is generally superior over conventional surfactant in term of surface activity. This is due to the distortion of water by hydrophobic groups. In Gemini surfactant two hydrophobic groups in single molecules are more disruptive than individual chain in conventional surfactant. 65

5 Fig. 4: Variation of surface tension versus log conc. at 25 O C Effectiveness is determined by the difference between interfacial tension values at CMC (ϒ CMC ) and the interfacial tension values measured for pure water at the appropriate temperature (ϒ 0 ). The most effective surfactant gives the greatest lowering of surface tension for given CMC. The values of surface tension at CMC, critical micelles concentration and effectiveness are shown in table 1. Table 1: Surface active properties of the Gemini surfactant at temp (25 o C) Sr. No. Parameters Values 1 Surface Tension 30.1 mn/m 2 Critical Micelle concentration mmoll -1 3 Effectiveness (π cmc ) 41.9 mn/m Performance Properties- Among the performance properties emulsifying power, wetting power, foaming power and stability, dispersion capability of product at different concentrations have been studied and results are shown in table Emulsifying power- Emulsifying power of the aqueous solutions of product was determined for water/liquid paraffin (light) system. Stable emulsion was formed using surfactant solution to oil in a ratio of 1:1 (volume:volume). At different concentration of the synthesized Gemini surfactant, a creamy emulsion of oil in water was observed. The more is the time required for clearing the two layers, the higher is the emulsifying power of the surfactant [Xu RF et al, 2012]. On storage during the steady state, it was observed that the creamy stability gradually decreases. This may be result of droplet break and not droplet formation. The emulsifying power of surfactant increases with concentrations as shown in table Wetting Performance-The wetting behaviors of the product synthesized was studied using the canvas disc method [McCutecheon JW 1950]. The time required to sink the canvas disc in surfactant solution was measured as wetting time. The minimum is the time required for sinking the disc, higher is the wetting power of surfactant. The wetting time decreases with increase in concentration as shown in table 2. The result shows that wetting performance of synthesized Gemini surfactant is much better even at low concentration Foaming power and stability-the most widely appreciated property of surface active substances in aqueous solution is their ability to promote the formation of foam and bubbles. These behaviors could be attributed to the physical nature and bubble formation [S. Warwel et al, 2004]. 66

6 The results obtained for synthesized Gemini surfactant shows high quality foam production. The foam produced from synthesized surfactant has thicker nature with small bubbles throughout the experimental period. The foaming power and stability increases with increase in concentration of synthesized product (table 2). Table 2: Emulsifying power, wetting time, foaming power, foaming stability of synthesized Gemini surfactant at different concentration Sr. No. Concentration of surfactant (0.1gm/100ml) Emulsifying power (minute) Wetting time (second) Foam volume(ml) at 30 second Foam volume(ml) at 300 seconds Dispersing capability [Zhu YP et al, 1990]-A surfactant possesses the ability to disperse the agglomerative solid particle, and this is called dispersibility. Generally, dispersibility is measured by its lime-soap dispersion ability. The lime soap dispersion capability of the synthesized gemini surfactant was measured as 28%. The smaller the LSDR %, the better is the dispersibility. It was found that the dispersion capability of synthesized surfactant is quite good. 3.3 Contact Angle Measurement [Erwin A. Vogler et al, 1992]-The dynamic contact angles of Glass slides, Steel slides, Teflon slides against diluted surfactant solution (0.1M) were determined as shown in table 3. These values of contact angle were lower than those obtained for pure water. Smaller the contact angle better is the wetting power. These value show that synthesized Gemini surfactant has very good wetting property. Table 3: Contact angle values of 0.1M synthesized Gemini surfactant with respect to different solid probes Sr. No. Solid probes Contact angle With respect to Distilled water Surfactant sol (0.1M ) 1 Glass Steel Teflon Solubilization Behaviour: A light-scattering technique was used to measure the solubilizing power of the prepared surfactant solutions at 28 O C using Hatch model 1/100 turbidity meter. Solubilizing power of different surfactant solutions was measured by dispersing paraffin oil as a nonpolar solute and 1-Heptanol as a polar solute. 1 gm of solute was mixed together with 100 ml of surfactant solution (0.5%) using rotary shaker at 240 rpm for different time interval (0, 2, 5, 10, 20, 30, 40, 50 and 60 minute) and turbidity was measured. Solubilization behavior of aqueous solution of non-ionic Gemini surfactant is represented in fig.5 (a) and (b) for different type of solutes (heptanol and paraffin oil as polar and non-polar solute respectively) at 28 O C. These figures show that the turbidity of the surfactant solutions was low at the beginning of the experiment (T= 0) but the turbidity of the system gradually increases with 67

7 shaking time. The solubilizing process depends on many variables, especially the nature of the solvent, alkyl chain length, head groups, concentration of solvent in solution and chemical structure of the solute Surfactant/paraffin oil system- Solubilizing power of synthesized Gemini surfactant for paraffin oil system is quite good as shown in fig.5 (a). This can be attributed to the fact that the amount of material solubilized increased with an increase in the size of the micelles. Hence any factor that causes an increase in either the diameter of the micelle or its aggregation number result in the increase of solubilization Surfactant/Heptanol solubilizing system- The solubilization behavior for the surfactant/heptanol system is shown in the fig. 5 (b). This solubilization behavior for the surfactant/heptanol system poorer than the behavior of the surfactant/paraffin oil system. This poor solubilization behavior indicates that emulsification is not the only interaction that took place between system components, but some other factor influence the solubilization process. This factor could have been an interaction between the two polar head in the different molecules [A. S. Mohamed et al, 2004]. Fig.5: (a) and (b) Solubilization behavior of the Non-polar (light Paraffin oil) and polar (Heptanol) solute respectively in an aqueous surfactant solution (0.5%) at 28 O C 4. CONCLUSION In the present study a new protocol for the synthesis of novel glycerol based non-ionic Gemini surfactant through an environmental friendly process have been described. Glycerol based nonionic Gemini surfactant has been successfully synthesized by using, 1, 6-dibromohexane as spacer. The compound is characterized by FTIR, 1 H-NMR and 13 C-NMR spectroscopy. The surface active properties like surface tension, critical micelle concentration, effectiveness have also been studied. The performance properties like emulsifying power, foaming power and stability, dispersion capability, wetting power, contact angle, solubilizing behaviour were also studied. It can be concluded that the new glycerol-based non-ionic Gemini surfactant exhibit generally good solubilizing and wetting behaviour. It appears to be a promising and valuable non-ionic surfactant. It can be used as an emulsifier, wetting agent and foaming agent. 68

8 ACKNOWLEDGMENT Authors are thankful to the UGC (University Grants Commission of the research grant for this research work [Project F.No /2012 (SR)]. India), for providing REFERENCES 1. S. K. Hait and S. P. Moulik (2012), Gemini surfactants: A distinct class of self-assembling Molecules, Current Science, 82 (9): R. Janardhan, V. Vijayabaskar and B. S. R. Reddy (2012), Synthesis and Characterization of Sulfonate Dimeric Malenised Soya Fatty Acid: A Novel Gemini Surfactant, J. Surface Sci. Technol., 28 (3-4): Wenjian Zhang, Liguo Zhou, and Zhaoyun Ding (2009), Synthesis and Performance of Nonionic Gemini Surfactant Di-Glycerol 2, 9-Dihexyldecanedioate, Journal of Dispersion Science and Technology, 30 (9): Aratani K., Oida T., Shimizu T., and Hayashu Y. (1998), Preparation and Properties of gemini surfactant from tartaric acid, Communications presented as a las Jornadas del Comite Espanol de la Detergencia, 28: Anno Wagenaar & Jan B. F. N. Engberts (2007), Synthesis of nonionic reduced-sugar bola amphiphiles and surfactants with an α,ω-diamin-(oxa) alkyl spacer, Science Direct Tetrahedron, 63: Wim D. Bossaert, Dirk E. De Vos, Wim M. Van Rhijn, Joren Bullen, Piet J. Grobet and Pierre A. Jacobs (1999), Mesoporous Sulfonic Acids as Selective Heterogeneous Catalysts for the synthesis of Monoglyceride, Journal of Catalysis, 182 (1): Sebastien Queste, Pierre Bauduin, Didier Touraud, Werner Kunz and Jean-Marie Aubry (2006), Short chain glycerol 1-monoethers-a new class of green solvo-surfactants, Journal of the Royal Society of Chemistry, Green Chem., 8 (9): B. S. Furniss, A. J. Hannaford, P. W. G. Smith, Austin R. Tatchell (1989), Vogel s Text book of practical organic chemistry, Addision Wesley Longman, Inc, pp L. M. Harwood, C. J. Moody and J. M. Percy (2011), second edition, Experimental Organic Chemistry, Standard and micro scale, Wiley Pvt. Ltd, India, pp Xu RF, Xu HJ, Xu H, Geng H, Chen L (2012), Synthesis and properties of 4,40-di(ntetradactyl) diphenylmethane disulfate salt, Appl Chem Ind 41: McCutecheon JW (1950), Synthetic detergents, McNair-Dorland s, New York, pp S. Warwel, F. Bruse and H. Schier (2004), Glucamine Based Gemini Surfactants: Gemini Surfactant from Long-Chain N-alkyl Glucamines and α, ω-diepoxides, Journal of surfactants and detergents, 7 (2): Erwin A. Vogler (1992) Practical Use of Concentration-Dependent Contact Angles as a Measure of Solid-Liquid Adsorption. 1. Theoretical Aspects, American Chemical Society, 8 (8): Zhu YP, Masuyama A, Okahara M (1990), Preparation and surface active properties of amphipathic compounds with two sulfate groups and two lipophilic alkyl chains, J Am Oil Chem. Soc 67: A. S. Mohamed, M. Z. Mohamad & D. A. Ismail (2004), Alinine-Based Surfactants: Synthesis and Some Surface Properties, Journal of Surfactant, 7(4):