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Frontiers of Agricultural Science and Engineering

Front. Agr. Sci. Eng.    2016, Vol. 3 Issue (1) : 46-54
Synthesis and characterization of castor oil-based polymeric surfactants
Xujuan HUANG1,2,He LIU1,*(),Shibin SHANG1,*(),Zhaosheng CAI2,Jie SONG3,Zhanqian SONG1
1. Institute of Chemical Industry of Forestry Products, Chinese Academy of Forestry, Key Laboratory of Biomass Energy and Material, National Engineering Laboratory for Biomass Chemical Utilization, Key and Laboratory on Forest Chemical Engineering, State Forestry Administration, Nanjing 210042, China
2. School of Chemical and Biological Engineering,Yancheng Institute of Technology, Yancheng 224051, China
3. Department of Chemistry and Biochemistry, University of Michigan-Flint, Flint, MI 48502, US
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Dehydrated castor oil was epoxidized using phosphoric acid as a catalyst and acetic acid peroxide as an oxidant to produce epoxidized castor oil (ECO). Ring-opening polymerization with stannic chloride was used to produce polymerized ECO (PECO), and sodium hydroxide used to give hydrolyzed PECO (HPECO). The HPECO was characterized by Fourier transform infrared, 1H and 13C nuclear magnetic resonance spectroscopies, gel permeation chromatography, and differential scanning calorimetry. The weight-average molecular weight of soluble PECO and HPECO were 5026 and 2274 g·mol-1, respectively. PECO and HPECO exhibited glass transition. Through neutralizing the carboxylic acid of HPECO with different counterions, castor oil-based polymeric surfactants (HPECO-M, where M= Na+, K+ or triethanolamine ion) exhibited high efficiency to reduce the surface tension of water. The critical micelle concentration (CMC) values of HPECO-M ranged from 0.042 to 0.098 g·L-1 and the minimum equilibrium surface tensions at CMC (gcmc) of HPECO-M ranged from 25.6 to 30.0 mN·m-1. The water-hexadecane interfacial energy was calculated from measured surface tension using harmonic and geometric mean methods. Measured values of water-hexadecane interfacial tension agreed well with those calculated using the harmonic and geometric mean methods.

Keywords epoxidized vegetable oil      ring-opening polymerization      interfacial tension      polymeric surfactant     
Corresponding Authors: He LIU,Shibin SHANG   
Just Accepted Date: 27 January 2016   Online First Date: 26 February 2016    Issue Date: 07 April 2016
 Cite this article:   
Xujuan HUANG,He LIU,Shibin SHANG, et al. Synthesis and characterization of castor oil-based polymeric surfactants[J]. Front. Agr. Sci. Eng. , 2016, 3(1): 46-54.
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Xujuan HUANG
Shibin SHANG
Zhaosheng CAI
Zhanqian SONG
Fig.1  The synthesis scheme for HPECO
Fig.2  Comparison of FT-IR spectra
Fig.3  1H NMR (a) and 13C NMR (b) of ECO and HPECO
Fig.4  GPC trace for soluble PECO and HPECO
Samples Mn × 105/(g?mol-1) Mw × 105/(g·mol-1) PDI (Mw/Mn)
Soluble PECO 2189 5026 2.30
HPECO 1949 2274 1.17
Tab.1  GPC of soluble PECO and HPECO
Fig.5  DSC curves for PECO and HPECO
Fig.6  Effect of HPECO-M concentration on the surface tension of water
HPECO-M CMC/(g·L-1) gcmc/(mN·m-1)
HPECO-Na+ 0.066 26.5±0.8
HPECO-K+ 0.042 25.6±0.7
HPECO-TEA+ 0.098 30.0±1.0
Tab.2  CMC and gcmc of HPECO-M
Fig.7  Effect of HPECO-M concentration on the water-hexadecane interfacial tension
HPECO-M gcmc/(mN·m1) ITmin/(mN·m1) Calculated interfacial tension/(mN·m1)
cSd GMmethod HM method
HPECO-Na+ 26.5 11.2±0.5 0.55 15.64 13.83
HPECO-K+ 25.6 10.4±0.7 0.55 15.58 13.60
HPECO-TEA+ 30.0 13.8±0.6 0.55 16.03 14.79
Tab.3  Calculated versus measured interfacial tension between HPESO-M surfactant and hexadecane
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