Phase Behavior of Ester Based Anionic Surfactants: Sodium Alkyl

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Applied Chemistry

Phase Behavior of Ester Based Anionic Surfactants - Sodium Alkyl Sulfoacetates Avinash Bhadani, Ananda Kafle, Taku Ogura, Masaaki Akamatsu, Kenichi Sakai, Hideki Sakai, and Masahiko Abe Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.9b00286 • Publication Date (Web): 29 Mar 2019 Downloaded from http://pubs.acs.org on March 31, 2019

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Industrial & Engineering Chemistry Research

Phase Behavior of Ester Based Anionic Surfactants - Sodium Alkyl Sulfoacetates Avinash Bhadani,*† Ananda Kafle,‡ Taku Ogura,†§ Masaaki Akamatsu,‡ Kenichi Sakai,†‡ Hideki Sakai,†‡ and Masahiko Abe*† †Research

Institute for Science and Technology, Tokyo University of Science, 2641 Yamazaki,

Noda, Chiba 278-8510, Japan. ‡

Department of Pure and Applied Chemistry, Tokyo University of Science, 2641 Yamazaki,

Noda, Chiba 278-8510, Japan. §

Research and Development Headquarters, Lion Corporation, 2-1, Hirai 7-Chome, Edogawa-

Ku, Tokyo 132-0035, Japan. ABSTRACT Ester based anionic surfactant - sodium lauryl sulfoacetate (SLSA) is one of the most important surface-active ingredients in several personal care products however no scientific report is available regarding its lyotropic and thermotropic phase behavior in water. In the present study, SLSA and its congener sodium myristyl sulfoacetate (SMSA) are investigated for their selfaggregation properties in aqueous system. Phase transition temperature of these surfactantwater mixtures is determined by differential scanning calorimetry (DSC). Their lyotropic and thermotropic phase behavior in water are investigated by polarized optical microscopy (POM), small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS). These surfactants predominantly exist as different types of self-assembled lamellar phases along with or without solid crystalline phases in aqueous system.

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1. INTRODUCTION Surface-active agents are employed in many consumer and industrial products and their ability to self-assemble into different types of soft materials is widely utilized by formulators to develop new products.1,2 In recent years, the isotropic micellar and lyotropic liquid crystalline phases formed by different types of ester based surfactants have been investigated in detail.3-7 While cationic surfactants demonstrate some distinctive characteristic properties, as apart from their utility in cleaning and hygiene products, they also find application in biotechnological application areas.8,9 On the other hand the anionic surfactants constitute major market share among the different types of surfactants and are principal essential ingredient of a wide range of industrial and consumer formulations.10 Sodium dodecyl sulfate (SDS), also known as sodium lauryl sulfate (SLS) is the most common conventional synthetic anionic surfactant molecule along with linear alkylbenzenesulfonate (LAB) and sodium laureth sulfate (SLES), which are important ingredient of countless formulations in personal care and household products such as detergents and cleaners, dish washing liquids, industrial cleaners, paints and coatings, rubber, polymer additives, etc.11-13 However, in recent years ester functionalized relatively more environmentally benign anionic surfactant - sodium lauryl sulfoacetate (SLSA) is increasingly becoming popular and is gradually replacing SDS in many application areas although the later is still the most popular surfactant molecule for several bulk application areas. Searching for “Sodium Lauryl Sulfoacetate” in SciFinder reveals that more than a hundred of patents have been filed since last decade for formulation containing SLSA as one of the important surface-active ingredient. Hikota and Meguro studied series of alkyl sulfoacetates and determined their cmc values, emulsifying power and foaming properties.14 Gad et al. further studied these surfactants for their self-aggregation properties by surface tension measurements.15 Prior studies have established that the SLSA is comparatively milder towards skin compared to other commercially available anionic surfactants.16,17 Most of the


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studies of sodium alkyl sulfoacetaes available in the literature mainly focus on concentrations just above their critical micelle concentration or studies carried in dilute aqueous solution. In recent years these surfactants have became very popular ingredient for several consumer and industrial formulations. They are currently being used in cleaning formulation,18 detergents,19 shampoo formulation,20 hair care formulation,21,22 transdermal topical formulations,23 oral care compositions,24 cosmetic formulations,25 pharmaceutical compositions26 etc. However information regarding their phase behavior is scarcely available in scientific literature. Comprehensive understanding of lyotropic and thermotropic phases formed by surfactants in water having specific characteristic, which influences the macroscopic properties of the system is very important in formulation chemistry. Knowledge about the phase behavior of surfactantwater systems is a preliminary step in designing a particular formulation based on a surfactant. The physical properties of self-assembled lyotropic phases change with respect to water concentration and temperature affecting the viscosity and the hardness of the system.27 Hence in the current manuscript we have investigated the lyotropic and thermotropic phase behavior of SLSA and SMSA by microscopy, calorimetric and scattering techniques.

2. MATERIALS AND METHODS

2.1. Materials. SLSA and SMSA were synthesized according to previously reported synthetic methodology.14,15 1-Dodecanol, 1-tetradecanol, bromoacetic acid, chloroacetic acid and thionyl chloride were purchased from TCI Chemicals. Sodium sulfite was purchased from Wako Pure Chemical Industries Ltd. Ultra pure water was used in all the experiments. 2.2. Differential Scanning Calorimetry DSC measurements were carried out on a Rigaku DSC-8230 instrument. Measurements were performed during a continuous temperature scan from 25 °C to 80 °C. About 3.0-3.3 mg of samples were sealed in aluminum sample pans and the heat flow was measured against alumina


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as a reference. Temperature scans from 25 to 80 °C was performed for each sample at rates of 3 Kmin-1.28-30 2.3. Polarized Optical Microscopy Appropriate amount of samples were mounted on glass slides with a coverslip placed on the top. The slides were observed under IMT-2 microscope (Olympus Optical Co. Ltd) through crossed polarizers at room temperature.31 The textures observed were transferred to a computer with the help of Moticam 2000 digital camera fitted on the eyepiece. The magnification of 300X was used for microscopic observations of the samples. The images were used to characterize the lyotropic phases inherent in the mixtures.32-34 2.4. SAXS/WAXS Measurements Samples were prepared in screw capped glass tubes by weighing appropriate surfactant and water. The tubes were sealed and kept at 80 ºC for 1 h, then vortexed for 10 min and centrifuged at 3500rpm for 30 min. The procedure was repeated three times and the samples were kept for 1 week to attain equilibrium. Measurements were performed using a SAXSess camera (Anton Paar, Austria) attached to a PW3830 laboratory X-ray generator with a long fine focus sealed glass X-ray tube (KR wavelength of 0.154 nm; PANalytical). The apparatus was operated at 40 kV and 50 mA. The SAXSess camera is equipped with focusing multilayer optics and a block collimator for an intense and monochromatic primary beam with low background, and a translucent beam stop for the measurement of an attenuated primary beam at zero scattering vector (q = 0). Samples were enclosed in vacuum-tight sampler. Sample temperature was controlled with a thermostatted sample holder unit (TCS 120, Anton Paar). The 2D scattering pattern was collected on an image plate (IP) detection system Cyclone (Perkin-Elmer, United State) and was finally integrated into one-dimensional scattering curves as a function of the magnitude of the scattering vector q = (4π/λ)sin(θ/2) using SAXSQuant software (Anton Paar,


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Austria), where θ is the total scattering angle and λ is the wavelength of the X-ray. All data were normalized to the same incident primary beam intensity for the transmission calibration and were corrected for background scattering from the capillary and the solvent.35-38 3. RESULTS AND DISCUSSION Ester based anionic surfactants - sodium alkyl sulfoacetates: SLSA and SMSA investigated in the present study is shown in Figure 1.

Figure 1. Molecular structure of SLSA and SMSA investigated in present study. The phase behavior of these surfactants in water is investigated by DSC, POM and SAXS/WAXS experiments. The phases formed by these surfactants were initially determined by POM (Figure 2) and further confirmed by SAXS/WAXS studies. At 25°C, lamellar gel phase (Lβ) and hydrated solid crystalline (Cr) phase coexist for both SLSA-water and SMSAwater systems (between 40-60 wt.%) and their co-existing phases were observed by POM. However, SLSA specifically exhibits a solid lamellar crystalline (LC) phase at 70wt.% in water at 25°C, while coexistence region of LC and Lβ is observed for SMSA in water at similar temperature and concentration.

Table 1: Phase transition temperature range and phases formed by SLSA-water and SMSAwater system at different surfactant concentration. Surfactant wt.% in water 40 wt.% SLSA

Phase transition Phases formed at d-spacing (nm) before range (°C) 25°C phase transition 34.4–41.8

Lβ + Cr

Lβ (3.02)


After phase transition

d-spacing (nm) after phase transition

L1 + Lα

Lα (4.39)

5


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40 wt.% SMSA

42.4–48.9

Lβ + Cr

Lβ (3.34)

L1 + Lα

Lα (5.06)

50 wt.% SLSA

34.6–47.4

Lβ + Cr

Lβ (3.06)

L1 + Lα

Lα (3.72)

50 wt.% SMSA

43.5–50.4

Lβ + Cr

Lβ (3.36)

Lα

Lα (4.22)

60 wt.% SLSA

37.9–56.2

Lβ + Cr

Lβ (3.05)

Lα

Lα (3.62)

60 wt.% SMSA

41.7–55.9

Lβ + Cr

Lβ (3.35)

Lα

Lα (4.08)

70 wt.% SLSA

45.1–67.3

LC*

LC (3.79)

Lα

Lα (3.53)

70 wt.% SMSA

45.8–69.3

LC*+Lβ

LC (4.26) Lβ (3.37)

Lα + LC

LC* (4.26) Lα (3.93)

*Traces of hydrated solid crystals were observed along with reported lamellar phases.

The phase behavior of the surfactant-water system was further studied by DSC experiments. The thermogram showed a broad endotherm for each individual surfactant-water system at certain temperature denoting the phase transition temperature (Figure 3). Above the phase transition temperature these surfactants system forms different kind of thermotropic phases depending upon the hydrophobic alkyl tail length and concentration of the surfactant in water. The different types of birefringent materials formed by these surfactants are shown in Table 1. Individual sample of 40 wt.% SLSA and SMSA in water formed co-existing Lβ and Cr phases at room temperature that were visible by POM (Figure 2a & 2i). 40 wt.% SLSA in water demonstrated endothermic peak in-between 34.4–41.8 °C (Figure 3a), while SMSA demonstrated endothermic peak in-between 42.4–48.9°C (Figure 3b) at same surfactant concentration. Above their respective phase transition temperature these surfactants formed micellar (L1) and lamellar liquid crystalline phase (Lα). SAXS profile and WAXS profile of SLSA and SMSA in water containing 40 wt.% surfactant concentration at 25°C (Figure 4a & 4c) and 50°C (Figure 4b & 4d) further confirmed existence of co-existing Lβ and Cr phases at room temperature and L1 and Lα phases above their respective phase transition temperature.


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Figure 2: POM images of SLSA-water and SMSA-water system captured at different surfactant concentration present in water. POM micrographs were observed at room temperature (25°C) and above their respective phase transition temperature. Bragg peaks with ratios of 1:2 visible in SAXS spectra denotes predominant existence of Lβ phases at 25°C for both 40 wt.% SLSA and SMSA in water. However WAXS diffraction profile showed a number of diffraction peaks indicating existence of highly crystalline material.39 The multiple diffraction peaks observed in WAXS diffractogram (Figure 5a & 5c) confirms the existence of the Cr phases at room temperature supporting the observation of coexisting Lβ and Cr phases observed by POM at 25°C (Figure 2a & 2i). The characteristic WAXS pattern for Lβ lamellar gel phase is observed as sharp peak at 14.28 nm-1 confirming existence of Lβ lamellar gel phase at room temperature.40,41 SAXS pattern for the same samples


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observed at 50°C, above their respective phase transition temperature demonstrate co-existence of L1 and Lα phases (Figure 4b & 4d). However the intensities of the second and third order peaks are too low to be observed in the system. Missing diffraction peaks in a lamellar system is not uncommon and has been previously reported by several research groups.42,43 The results are in accordance with the POM observations recorded for SLSA and SMSA for 40 wt.% above their respective phase transition temperature as Lα phases are visible for both the samples (Figure. 2b & 2j).

Figure 3: DSC curves obtained for (a) SLSA and (b) SMSA at different surfactant concentration. Evaluation of 50wt.% samples of SLSA and SMSA in water by POM also demonstrated coexistence of Lβ and Cr phases at room temperature (Figure 2c & 2k), which was further confirmed by SAXS (Figure. 4e & 4g) and WAXS (Figure. 5e & 5g) analysis results. Both the sample behaves differently above their respective phase transition temperatures as SLSA formed mixed L1 and Lα phases predominantly consisting of the later phase (Figure. 4f). However, 50wt.% SMSA exists as Lα phase above its phase transition temperature as evident by POM images (Figure. 2l) and SAXS profile (Figure. 4h). The results demonstrate that 50wt.% SLSA containing 12 carbon hydrophobic tail are able to co-exist as L1 and Lα phases above their phase transition. In contrast SMSA containing 14 carbons hydrophobic tail are able


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to selectively form thermotropic Lα phase at same concentration. While it is not possible to determine L1 phase by POM analysis and only Lα phases are visible (Figure 2d), the 50wt.% SLSA at 55°C shows a broad peak between 0.9 to 1.5 nm-1 confirming existence of L1 phase above its phase transition temperature. The disappearance of multiple diffraction peak and appearance of broad peak close to ∼13 nm-1 in WAXS region strongly suggests existence of Lα phases in both the samples above their phase transition temperature (Figure. 5f & 5h).44

Figure 4: SAXS patterns observed for SLSA and SMSA in water at different concentrations and temperatures. 60wt.% samples of SLSA and SMSA in water contain both Lβ and Cr phases at room temperature as evident by POM observations (Figure. 2e & 2m). These samples exist as


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thermotropic Lα phase above their respective phase transition temperature (Figure. 2f & 2n). The characteristic peaks for Lβ having Bragg peaks in ratios of 1:2 are visible in SAXS profile (Figure. 4i & 4k) along with the characteristic peak for Lβ phase in WAXS pattern (Figure. 5i & 5k) at 25°C for both SLSA and SMSA samples. Multiple diffraction peaks are also observed in WAXS diffractogram, which confirms the existence of the Cr phases along with Lβ phase at room temperature. Similarly, characteristic peaks for thermotropic Lα phase is evident for 60wt.% samples of SLSA and SMSA in SAXS profiles (Figure. 4j & 4l) and WAXS profiles (Figure. 5j & 5l) at 65°C, above their phase transition temperatures. The position of Bragg peaks obtained for lyotropic Lβ phase at room temperature and thermotropic Lα phase above the phase transition temperatures significantly differs for both SLSA and SMSA.45 The phases formed by SLSA and SMSA at 70wt.% in water significantly differs, as the former is able to exist as solid lamellar crystalline (LC) phase (Figure. 2g) while the later co-exits as Lβ and LC phases (Figure. 2o) at room temperature. LC phase formed by 70wt.% SLSA demonstrates Bragg peaks of 1:2:3 ratios in SAXS profile. Traces of hydrated crystals of SLSA were also detected at 70wt.% in water at 25°C. Unlike other samples containing lower surfactant concentration, the characteristic peak for Lβ is absent in WAXS profile of SLSA (Figure. 5m). At higher temperature above its phase transition temperature SLSA selectively forms thermotropic Lα liquid crystalline phase, which is evident by recorded POM images of the sample at 75°C (Figure. 2h).46 The SAXS profile (Figure. 4m) and WAXS pattern (Figure. 5m) recorded at 75°C for the 70wt.% SLSA further confirmed the results observed by POM as the ratio of the observed Bragg peaks in SAXS and appearance of broad peak in WAXS confirmed existence of thermotropic Lα liquid crystalline phase at high temperature.47 SMSA behaves differently compared to its congener SLSA at 70wt.% in water as the former co-exits as Lβ and LC phases at room temperature and as mixed Lα and LC phases above its phase transition temperature. Hence two distinct Bragg peaks are visible in SAXS profile for this


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sample with ratios of 1:2:3 at 25°C (Figure. 4n) and at 75°C (Figure. 4p) denoting Lβ and LC phases at room temperature and Lα and LC phases above its phase transition temperature respectively. In addition to the observed phases of SMSA at room temperature, traces of solid crystals were also observed at room temperature.

Figure 5: WAXS patterns of SLSA and SMSA observed in water at different surfactant concentrations. The experiments were performed at room temperature (25°C) and above the respective phase transition temperature of the individual surfactant-water system. The repeat distances (d values) of the different types of lamellar phases (lamellar gel Lβ, lamellar liquid crystalline Lα and solid lamellar crystalline LC phases) formed by the SLSA


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and SMSA at different surfactant concentration can be determined with certainty from the observed q values in SAXS profile. The repeat distances can be obtained by using the equation d = 2π/q where q is the first order Bragg peak position observed in SAXS profile.48 The d values for the lyotropic Lβ phases formed by the SLSA and SMSA in water does not change with change in surfactant concentration and has been found to be nearly constant for selfassembled individual surfactant molecule in water (Table 1). However this value decreases with increase in concentration of surfactant for thermotropic Lα phases formed by these surfactants above the phase transition temperature (Figure 6). The larger d spacing observed for the SLSA and SMSA at 40wt.% above their respective phase transition temperature can be explained on the basis of availability of excess of water. Both the surfactants under investigation are able to form mixed L1 and Lα phases above their phase transition temperature and in the presence of excess of water Lα phases formed may swell by absorbing additional water molecules in the lamellar channel.

Figure 6: (a) The d spacing versus surfactant concentration plot for SLSA and SMSA. (b) 2D graphical representation showing decreasing d spacing with increasing surfactant concentration for thermotropic Lα phases formed by surfactant. The d values for all the lamellar phases formed by SLSA containing 12-carbon hydrocarbon chain are lower compared to SMSA containing 14-carbon hydrocarbon chain since the


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repeating distances for lamellar phases always increases with increasing hydrophobic alkyl chain length. Also the calculated d values for lyotropic Lβ phases are smaller compared to thermotropic Lα phases for both the ester based anionic surfactants investigated in the current studies (Table 1). At the higher surfactant concentration (70 wt.%) SLSA exist as solid crystalline phase at room temperature predominantly consisting of lamellar solid crystalline phase LC with d value of 3.79 nm. In contrast the SMSA at 70 wt.% at 25°C consist of mixed LC phase and Lβ gel phase. Since this sample predominantly consist of lamellar solid crystalline LC with Lβ gel phase (below the phase transition temperature), and mixed Lα and LC phases (above the phase transition temperature), it is possible to compare the d spacing of three different lamellar phases formed by at 70 wt.% SMSA in water below and above its phase transition temperature.

Figure 7: Three different types of lamellar phases formed by 70 wt.% SMSA in water characterized by SAXS and WAXS patterns. LC and Lβ lamellar phases co-exist at 25°C, while Lα and LC lamellar phases co-exist at 75°C. Figure 7 shows different types of lamellar phases formed by 70 wt.% SMSA in water at different temperature. As the solid crystalline LC phases co-exists with other lamellar phases both at 25°C and 75°C. The d spacing of the characterized LC phases determined both below


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and above its phase transition temperature is found to be 4.26 nm indicating that the LC phases present in the sample do not undergo thermal change upon raising the temperature for 70 wt.% SMSA in water. The d spacing for Lβ phase present at the 70 wt.% SMSA in water is determined to be 3.37 nm at 25°C and repeating distance for these phases formed at different surfactant concentration of SMSA remains constant. In contrast the d spacing for Lα phase formed at 75°C (above phase transition temperature) as shown in Figure 7 is greater compared to Lβ phase. CONCLUSION: Ester based anionic surfactants - SLSA and SMSA are investigated for their lyotropic and thermotropic phase behavior in water system. The phase transition temperature of the surfactants-water system is determined by DSC experiments and the phases formed by these surfactants in aqueous system below and above their respective phase transition temperature are investigated in detail by POM, SAXS and WAXS scattering techniques. These surfactants exits as mixed Lβ and Cr phases or mixed LC and Lβ phases or as LC phase at room temperature. At higher temperature above their respective phase transition temperature they either exists as mixed micellar and Lα phase or singly as Lα phase or co-exists as mixed LC and Lα phase depending upon both the hydrophobic tail length and concentration of surfactant present in water. The repeating distance (d value) of different kind of lamellar phases formed by these surfactants greatly differ from one another. The d spacing of Lβ phases formed at room temperature nearly remains constant for each particular surfactant irrespective of the surfactant concentration present in water. However d spacing values of Lα phases formed by these surfactants above their respective phase transition temperature decreases with increase in surfactant concentration. The detailed phase analysis of lyotropic and thermotropic phases formed by SLSA and SMSA will be useful to interdisciplinary researchers and will help in development of various new products based on these surfactants.


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AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] (Prof. Masahiko Abe) [email protected] (Dr. Avinash Bhadani) ORCID Masahiko Abe: 0000-0001-6255-316X Avinash Bhadani: 0000-0002-4981-3083 Notes The authors declare no competing financial interest. ACKNOWLEDGEMENTS Avinash Bhadani is thankful to Tokyo University of Science and Acteiive Research & Development Company, Japan for research support. SUPPORTING INFORMATION The Supporting Information is available free of charge on the ACS Publications website at DOI: xx.xxxx/acs.iecr.xxxxxxx. POM images demonstrating different phases formed by the SLSA and SMSA in water at different surfactant concentration and temperature. REFERENCES (1) Hargreaves, A. E.; Hargreaves, T. Chemical formulation: An overview of surfactant-based preparations used in everyday life; Royal Society of Chemistry: 2003; Vol. 32. (2) Laughlin, R. G. The aqueous phase behavior of surfactants; Academic press: London, 1994; Vol. 6.


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