←BACK

Research Article

 

Bentonite-Based Nano Organic Clay Using Chalcone and Azo Dye as Organophilic Reagents

 

Manar Ghyath Abd-Almutalib Al-Mosawy *, Emad Abbas Jaffar Al-Mulla *, Majed Jari Mohamad

 

Department of Chemistry, Faculty of Science, University of Kufa, P.O. Box 21, An-Najaf 54001, Iraq.

 

* Corresponding authors. Email: manarghyth@yahoo.com; imad.almulla@uokufa.edu.iq

 

Received: Apr. 25, 2017; Accepted: May 26, 2017; Published: Jun. 5, 2017

 

Citation: Manar Ghyath Abd-Almutalib Al-Mosawy, Emad Abbas Jaffar Al-Mulla, and Majed Jari Mohamad, Bentonite-Based Nano Organic Clay Using Chalcone and Azo Dye as Organophilic Reagents. Nano Biomed. Eng., 2017, 9(2): 124-128.

DOI: 10.5101/nbe.v9i2.p124-128.

 

Abstract

Organclays (OBNTs) were prepared using two new organic surfactants including 3-(4-aminophenyl)-1-(4-chlorophenyl)prop-2-en-1-on (CH) synthesized from a Claisen–Schmidt condensation reaction between p-aminoacetophenone and p-chlorobenzaldehyde; and 4-((4-nitrophenyl)diazenyl)-N-(pyrimidin-2-yl) (AZ) prepared from reaction of sulfadiazine and p-nitoaniline. Organclays OBNTs were characterized by Fourier transform infrared spectroscopy (FTIR) to evaluate the incorporation of surfactants in bentonite. The X-ray diffraction (XRD) technique was utilized to indicate the basal spacing of the treated clay as a measure of susceptibility of new organoclays. The FTIR and XRD results showed that the OBNTs were successfully incorporated in the layers of bentonite clay. Thermogravimetric analysis (TGA) was also used to determine thermal stability. An enhancement in stability was observed in OBNTs compare to pure bentonite. OBNTs prepared in this study can be used to produce disposable packaging a promising polymer nanocomposite.

 

Keywords: Sodium bentonite; Modification; Surfactants; Organic cations

 

Introduction

Bentonite, which is predominantly amontmorillonitic clay, is characterized by one Al octahedral sheet placed between two Si tetrahedral sheets. The isomorphous substitution of Al3+ for Si4+ in the tetrahedral layer and Mg2+ for Al3+ in the octahedral layer results in a net negative surface charge on the clay. This charge imbalance is offset by exchangeable cations typically Na+ and Ca2+at the clay surface. The layered structure of the clay allows expansion after wetting. Na+ and Ca2+ are strongly hydrate in the presence of water, resulting in ahydrophilic environment at the clay surface [1]. However, cation-exchange reaction have been traditionally exploited as an effective method  to replace these inorganic ions with organic cationic surfactant molecules, which intercalate into the clay gallery, resulting in expansion of the interlayer spacing and leading to an increase in the basal spacing. These organic cations render the surface of the clay mineral hydrophobic, leading to the increase of the clay wetttability and providing favourable interactions with organic molecules. Both organic-modified and unmodified clays have been used for different industrial applications such as rheological additives , thickeners in coating products glues, plastisols, drilling fluids and cosmetics [2,3]. Recently, clays were used in the field of materials science such as solid phase polymeric nanocomposites. In the 1990s, the use of organically modified clays in the polymer-clay nanocomposites has attracted researchers into this area of materials science and technology [4]. The organic modification of clay minerals leads to a decrease in surface energy making clays compatible with polymers. The surface energy of clay minerals and polymer can be determined from contact angle measurements [5]. Melt processed nylon 6-clay nanocomposites have been prepared using organoclay [6]. It was reported that, based on X-ray diffraction analysis, various arrangement of alkyl chains in organoclays had proposed. Novel organomontmorillonites have been synthesized and characterized using  different ammonium compounds [7-8]. In this study, two new different ammonium compounds 3-(4-aminophenyl)-1-(4-chlorophenyl)prop-2-en-1-on (CH) and 4-((4-nitrophenyl)diazenyl)-N- (pyrimidin-2- yl ) (AZ) were used to modify the compatibility of bentonite clay. These organoclays can be used in both medical and industrial applications specially in both promising polymer and biopolymer nanocomposites.

 

Experimental

Material

Hydrochloric acid from J. T. Baker, USA. Sodium hydroxide was obtain from merck, British. p-aminoacetophenone and p-chlorobenzaldehyde were obtained from Fluka, Germany.

 

Characterization

XRD analysis

The X-ray diffraction (XRD) study was carried out using a Shimadzu XRD 6000 diffractometer with Cu K radiation (k = 0.15406 nm). The diffractogram was scanned in the ranges from 2 to 10at a scan rate of 1/min.

 

FTIR spectroscopy

The fourier transform infrared spectroscopy (FTIR) spectra of the blends samples were recorded by the FTIR spectrophotometer (Perkin Elmer FTIR-Spectrum BX, USA) using KBr disc technique.

 

NMR techniques

1H-NMR (nuclear magnetic resonance) and 13C-NMR  spectra were obtained with Bruker, Ultra Shield 300 MHz and 75MHz , using dimethyl sulfoxide (DMSO) as solvent and transcranial magnetic stimulation (TMS) as an interanal standard.

 

TGA analysis

Thermogravimetric analysis (TGA) was recorded by thermal gravimetric analyzer, STA PT-1000 linseis TGA, Germany.

 

Preparation of chalcone [9]

0.5 g (0.002 mol) p-aminoacetophenone and 1 mmol p-chlorobenzaldehyde, were mixed with aqueous solution 10% NaOH. 0.5 mL of 99% EtOH was then added to the mixture. The resulting mixture was stirred at room temperature for 4hrs, and then poured in to ice water. After that, 10% HCl solution was added to the product. The solid formed was filtered then washed with ethanol and water at a ratio of 10 : 5. Recrystallization from 99% ethanol afforded produced pure chalcone (67% yield, yellow solid, m.p. 160 165 ̊C ).

 

Preparation of azo [10]

2 gm (0.0145 mol) of 4- nitro aniline was dissolved in 3 mL of concentrated hydrochloric acid and 15 mL of distilled water. The mixture was cooled at 0-5  ̊ C in ice-water bath, then 0.9 g (0.0145 mole) of a solution of sodium nitrite was dissolved in 5 mL of distilled water and then cooled at 0-5 ̊ C. This solution was added a drop wise to the mixture with stirring at the same temperature. Design amount of diazonum salt solution was added portion wise to solution of 3.62 g (0.0145 mol) sulfadiazine in distilled water with 1.5 g of sodium hydroxide dissolved in 100 mL distilled water. The pH was maintained with 6 - 7 and temperature at 0 - 5  ̊C. The mixture was stirred for 30 min and then left over night. The product was precipitated and filtered, washed well with sodium bicarbonate and distilled water under-crystallized from ethanol (yield 72% , brown solid, m.p. 193 - 198 ̊C).

 

Preparation of organoclays (OBNT) [11]

Sodium Bentonite (Na-BNT) 4.00 g was stirred vigorously in 600 mL of hot distilled water for 1 h to form a clay suspension. Subsequently, 4.50 g  of both CH and AZ, which had been dissolved in 400 mL of hot water and 16.00 mL concentrated hydrochloric acid was added into the clay suspension. After being stirred vigorously for 1 h at 80 ̊C, the organoclay suspension was filtered and washed with distilled water until no chloride was detected with a 1.0 mol silver nitrate solution. It was then dried at 60 ̊C for 72 h. The dried organoclay was ground until the particle size was 100 μm [12-13]. Scheme 1 shows the structures of CH and AZ used to prepare organoclays.

 

D:\xwu\Nano Biomedicine and Engineering\Articles for production\排版\9(2)\0018 校订中,有TOC\figs\mgs1.jpg

Scheme 1 The structures of (a) CH; and (b) AZ.

 

Results and Discussion

XRD analysis

The alkyl ammonium cation exchange enables the conversion of the hydrophilic interior clay surface into the hydrophobic surface and consequently increase the layer distance aswell [14]. In this study, Na-BNT was surface treated with CH and AZ as intercalation agent through cation exchange process. The cationic head groups of the intercalation agent molecule would preferentially reside at the layer surface and the tail of the compound will radiate a ways from the surface. The presence of these chains in the galleries makes the originally hydrophilic silicate to organophilic and thus increase the layer-to-layer spacing of Na-BNT [15]. The organoclays prepared in this work, 3-(4-aminophenyl)-1-(4-chlorophenyl)prop-2-en-1on-BNT (CH-BNT) and 4-((4-nitrophenyl)diazenyl)-N-(pyrimidin-2-yl)-BNT (AZ-BNT), were investigated using XRD measurements in the 2ϴ ranges from 2 10 ͦ. Na-BNT shows diffraction peak at 2 ϴ = 7.0762 which assigns to the interlayer distance of the natural bentonite with a basal spacing of 1.25 nm [16]. After the ion exchange reaction, the basal spacing (d001value) increases from 1.25 (Na-BNT) to 1.76 and 1.77  for CH-BNT and AZ-BNT, respectively (Fig.1). Diffraction angle and basal spacing of bebtonite and its modification with different organic cations suggested that CH and AZ have been intercalated into the Na-BNT galleries. The results  were summarized in Table 1.

 

D:\xwu\Nano Biomedicine and Engineering\Articles for production\排版\9(2)\0018 校订中,有TOC\figs\mgt1.jpg

Fig. 1 The XRD patterns of (a) Na-BNT; (b) CH-BNT; and (c) AZ-BNT.

 

Table 1 Diffraction angle and basal spacing of bebtonite and its modification with different organic cations

Sample

Exchanged cation

2 θ (°)

d (001) spacing (nm)

Bentonite

Na +

7.08

1.25

CH

C15H9CLO NH3+CH+

4.99

1.77

AZ

C16H9N5O4SNH3+AZ+

5.01

1.76

 

 

 

 

 

 

 

FTIR spectroscopy

FTIR is a useful technique to verify the presence of CH and AZ in the clay. Fig. 2 shows the FTIR spectra of Na-BNT, CH and CH-BNT, and Fig. 3 shows the FTIR spectra of Na-BNT, AZ and AZ BNT. In Fig. 3, FTIR of the Na-BNT shows two peaks, which correspond to Si-O stretching at 1047 cm‾1 and interlayer water deformation vibration at 1645 cm‾1 [17,18]. The peak at 3628 cm‾1 was from the O-H stretching vibration. The peaks at 2850 - 2920 cm‾1 and 2872 - 2939 cm‾1 correspond to the presence of the CH asymmetric and symmetric stretching vibration for CH-BNT and AZ-BNT, respectively. In the spectra of CH-BNT and AZ-BNT, the absorption bands at 3626 and 3640 cm‾1 indicate the presence of free O-H stretching and at 1091 and 1109 cm‾ 1correspound to C-N stretching [19, 20]. In addition to the bands of the original Na-BNT, the band at 1490 and 1438 cm‾1 suggests the existence of the ammonium ion. Therefore, these results indicate that of CH and AZ were successfully intercalated in the silicate layers.

 

D:\xwu\Nano Biomedicine and Engineering\Articles for production\排版\9(2)\0018 校订中,有TOC\figs\mgt2.jpg

Fig. 2  FTIR Spectra of (a)Na-BNT; (b) CH; and (c) CH-BNT.

 

D:\xwu\Nano Biomedicine and Engineering\Articles for production\排版\9(2)\0018 校订中,有TOC\figs\mgt3.jpg

Fig. 3 FTIR Spectra of (a)Na-BNT; (b) AZ; and (c) AZ-BNT.

 

NMR technique

Fig. 4 shows 1H-NMR spectra of CH and AZ, while 13C-NMR spectra of CH and AZ are shown in Fig. 5. 1H-NMR (300 MHz, DMSO) appearance of multiple signals at the site 6.3-7.8 ppm corresponds to the protons of benzene rings. The peak at the site 5.3 ppm refers to the protons of NH2, and the appearance of signals at the site 7.5-7.9 ppm corresponded to the protons of CH=CH. 1H-NMR spectra of AZ appearance of multiple signals at the site 7.6 -8.5 ppm was due to the protons of benzene rings. The peak at 6.5 ppm corresponded to the protons of NH2, and the appearance of signals at the site 11.32 ppm was due to the protons of NH in sulfadiazine. The 13C-NMR (75 MHz, DMSO) (Fig. 3(a)) appearance of multiple signals at the site 114.-130.6 ppm was due to the carbons of benzene rings. The peak at 189.7 ppm refered to the carbon of C=O, and the appearance of signals at the site 145.2-121.3 ppm corresponded to the carbon of CH=CH. The peak at around 2.5 ppm corresponded to DMSO as a solvent. 13C-NMR spectra of AZ (Fig. 3(b)) shows multiple signals at the site 114.3 -169.3 ppm which were due to the carbons of benzene rings.

 

 

D:\xwu\Nano Biomedicine and Engineering\Articles for production\排版\9(2)\0018 校订中,有TOC\figs\mgt4.jpg

Fig. 4 1H-NMR spectra of (a) CH; and (b) AZ

 

D:\xwu\Nano Biomedicine and Engineering\Articles for production\排版\9(2)\0018 校订中,有TOC\figs\mgt5.jpg

Fig. 5 13C-NMR spectra of (a) pure CH; and (b) pure AZ.

 

TGA analysis

TGA graph shows the curves of weight loss for increasing temperatures of Na-BNT, CH-BNT and  AZ-BNT (Fig. 6). The TGA curves gave information on the structure of the intercalating molecules by the weight loss steps. Thermal degradation of BNT was shown to be before 200 ̊C because of the volatilization of water adsorbed on the external surfaces of the BNT and water inside the interlayer space. The BNT contained water due to the hydrated sodium Na+ cations intercalated inside the clay layers. The presence of alkylammonium groups within the BNT interlayer spacing lowered the surface energy of the inorganic structure and would transform organophobic materials to organophilic ones. The major difference between the thermogram of the unmodified clay and that of the organoclay was that the organic constituents in the organoclay decompose were in the range from 180 to 500 ̊C.

 

D:\xwu\Nano Biomedicine and Engineering\Articles for production\排版\9(2)\0018 校订中,有TOC\figs\mgt6.jpg

Fig. 6 TGA graph of (a) Na-BNT; (b) CH-BNT; and (c) AZ-BNT.

 

Conclusions

Based on the results of this study, we concluded that the ammonium cations from CH and AZ ccould be successfully incorporated in the bentonite clay, and that the basal spacing of the bentonite clay increased as a result of incorporating CH and AZ. We also found that the new organoclay could be susceptible to produce polymer nanocomposites, and that the thermal stability was enhanced by incorporation of clay into CH and AZ.

 

References

  1. S. Yun-Hwei, Preparations of organobentonite using nonionic surfactants. Chemosphere, 2001, 44: 989-995.
  2. A.M. Motawie, M.M. Madany, A.Z. El-Dakrory, et al., Physico-chemical characteristics of nano-organobentonite prepared using different organo-modifiers. Egy. J. Petroleum., 2014, 23: 331–338.
  3. W.F. Jaynes, S.A. Boyd, Clay mineral type and organic compound sorption by hexadecyltrimethyl ammonium exchanged clays. Soil. Sci. Soc. Am. J., 1991,55: 43-48.
  4. J. Zhang, C.A. Wilkie, Preparation and flammability properties of polyethylene-clay nanocomposites. Polym. Degrad. stability, 2003, 80: 163-169.
  5. M. Maiti, A.K. Bhowmick, Structure and properties of some novel fluorolastomer/clay nanocomposites with special reference to their interaction.  J. Appl. Polym. Sci.2005, 44:162-176.
  6. E.A.J. Al-Mulla, Preparation of polylactic acid/epoxidized palm oil/fatty nitrogen compounds modified clay nanocomposites by melt blending. Polym. Sci - Series A., 2011, 53: 149-157.
  7. M.A. Motawie, N.M. Ahmed, S.M. ElMesallamy, et al., Unsaturated polyesters/layered silicate nanocomposites: Synthesis and characterization. IOSR J. of Appl. Chem., 2014, 7(10):34-43.
  8. S.M.M. Al-Mutoki, B.A.K. Al-Ghzawi, and A.A. Abdullah, et al., Synthesis and characterization of new epoxy/titanium dioxide nanocomposite. Nano Biomed. Eng., 7 (4), 135-138.
  9. S.A. Sadiq, E.M. Atiyah, and A.T. Numan, Synthesis and characterization of new bidentatechalcone ligand type (NO)and its MnІІ, CoІІ, NiІІ and CuІІ complexes with study of their antibacterial activity. Diyala J. Pure Sci.,2015, 11(3): 2222-2235.
  10. F.W. Salman, S.W. Radhi, and A.M. Jodh, Preparation and study antibacterial activity of a new polymer. J. of Babylon Pure Appl. Sci., 2015, 2:23-31.
  11. E.A.J. Al-Mulla, A.H. Suhail, and A.A. Saadon, New biopolymer nanocomposites based on epoxidized soybean oil plasticizedpoly(lactic acid)/fatty nitrogen compounds modified clay: Preparation and characterization. Ind. Crops Prod.., 2011,33: 23–29.
  12. E.A.J. Al-Mulla, W.M.Z. Yunus, N.A. Ibrahim, et al., Enzymatic synthesis of fatty amides from palm olein. J. Oleo. Sci.,2010, 59(2): 157–160.
  13. E.A.J. Al-Mulla, W.M.Z. Yunus, and N.A. Ibrahim, Epoxidizedpalmoil plasticized polylactic acid/fatty nitrogen compound modifiedclaynanocomposites: Preparation and characterization. J. Polym. Comp.,  2010, 18(8):451–460.
  14. W.M.Z. Yunus, N.A.B. Ibrahim, and M.Z.A. Rahman, Difatty acyl urea from corn oil: Synthesis and characterization. J. Oleo Sci.,2010, 59: 157–160.
  15. Y.J. Phua, W.S. Chow, and Z.A. MohdIshak, Organomodification of montmorillonite and its effects on the properties of poly(butylene succinate) nanocomposites. Polym. Eng. Sci., 2013,53: 1947–1957.
  16. B.A. Mansor, H.H. Wisam, N.I. Azowa. Modification of  montmorillonite by new surfactants. J. of Eng. Appl. Sci., 2009, 4(3):184-188.
  17. F.H.J. Al-Shemmari, E.A.J. Al-Mulla, and A.A. Rabah, A comparative study of different surfactants for natural rubber clay nanocomposite preparation. Rendiconti Lincei. 25 (3), 409-413.
  18. L. Guo, S. Wu, and F. Zeng, Synthesis and Fluorescence property of terbium complex with novel Schiff-base macromolecular legend. Eur. Polymer J., 2006, 42: 1670 – 1675.
  19. E. Ramachandranl, K. Baskaran, and S. Natarajan, XRD, thermal, FTIR and SEM studies on gel grown gamma-glycine crystals. Crys. Res. Tec.,  2007, 42: 73-77.
  20. S.M.M. Al-Mutoki, A.G. Wadday, and A.A. Abdullah, Effect of nano TiO2 dopant on electrical properties of SR8100/nano TiO2 PMNC. Results Phys.,2016, 6: 551-553.

 

Copyright© 2017 Manar Ghyath Abd-Almutalib Al-Mosawy, Emad Abbas Jaffar Al-Mulla, and Majed Jari Mohamad. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

 

Nano Biomedicine and Engineering.

Copyright © Shanghai Jiao Tong University Press