Please wait a minute...

Frontiers of Agricultural Science and Engineering

Front. Agr. Sci. Eng.    2016, Vol. 3 Issue (1) : 46-54     https://doi.org/10.15302/J-FASE-2016083
RESEARCH ARTICLE |
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
Download: PDF(715 KB)   HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks
Abstract

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.
 URL:  
http://journal.hep.com.cn/fase/EN/10.15302/J-FASE-2016083
http://journal.hep.com.cn/fase/EN/Y2016/V3/I1/46
Service
E-mail this article
E-mail Alert
RSS
Articles by authors
Xujuan HUANG
He LIU
Shibin SHANG
Zhaosheng CAI
Jie SONG
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
1 Meier M A R, Metzger J O, Schubert U S. Plant oil renewable resources as green alternatives in polymer science. Chemical Society Reviews, 2007, 36(11): 1788–1802
https://doi.org/10.1039/b703294c
2 Wang A L, Chen L, Xu F, Yan Z C. Phase behavior of glycerol trioleate-based ionic liquid microemulsions. Journal of the American Oil Chemists' Society, 2015, 92(1): 133–140
https://doi.org/10.1007/s11746-014-2565-4
3 Kiatsimkul P P, Suppes G J, Sutterlin W R. Production of new soy-based polyols by enzyme hydrolysis of bodied soybean oil. Industrial Crops and Products, 2007, 25(2): 202–209
https://doi.org/10.1016/j.indcrop.2006.10.001
4 Ferreira G R, Braquehais J R, da Silva W N, Machado F. Synthesis of soybean oil-based polymer lattices via emulsion polymerization process. Industrial Crops and Products, 2015, 65: 14–20
https://doi.org/10.1016/j.indcrop.2014.11.042
5 Cermak D M, Cermak S C, Deppe A B, Durham A L. Novel α-hydroxy phosphonic acids via castor oil. Industrial Crops and Products, 2012, 37(1): 394–400
https://doi.org/10.1016/j.indcrop.2011.12.018
6 Compton D L, Laszlo J A, Evans K O. Phenylpropanoid esters of lesquerella and castor oil. Industrial Crops and Products, 2015, 63: 9–16
https://doi.org/10.1016/j.indcrop.2014.10.030
7 Ogunniyi D S. Castor oil: vital industrial raw material. Bioresource Technology, 2006, 97(9): 1086–1091
https://doi.org/10.1016/j.biortech.2005.03.028
8 Guner F S. Castor oil dehydration kinetics. Journal of the American Oil Chemists' Society, 1997, 74(4): 409–412
https://doi.org/10.1007/s11746-997-0098-9
9 Nezihe A, Eliff D, Özlem Y, Tunçer E A. Microwave heating application to produce dehydrated castor oil. Industrial & Engineering Chemistry Research, 2011, 50(1): 398–403
https://doi.org/10.1021/ie1013037
10 Bantchev G B, Kenar J A, Biresaw G, Han M G. Free radical addition of butanethiol to vegetable oil double bonds. Journal of Agricultural and Food Chemistry, 2009, 57(4): 1282–1290
https://doi.org/10.1021/jf802774g
11 Lowe A B. Thiol-ene “click” reactions and recent applications in polymer and materials synthesis: a first update. Polymer Chemistry, 2014, 5(17): 4820–4870
https://doi.org/10.1039/C4PY00339J
12 Liu Z S, Doll K M, Holser R A. Boron trifluoride catalyzed ring-opening polymerization of epoxidized soybean oil in liquid carbon dioxide. Green Chemistry, 2009, 11(11): 1774–1780
https://doi.org/10.1039/b915742p
13 Li Y H, Wang D H, Sun X S. Copolymers from epoxidized soybean oil and lactic acid oligomers for pressure-sensitive adhesives. RSC Advances, 2015, 5(35): 27256–27265
https://doi.org/10.1039/C5RA02075A
14 Cavusoglu J, Cayli G. Polymerization reactions of epoxidized soybean oil and maleate esters of oil-soluble resoles. Journal of Applied Polymer Science, 2015, 132(7): 41457
https://doi.org/10.1002/app.41457
15 Chaudhary B I, Nguyen B D, Smith P, Sunday N, Luong M, Zamanskiy A. Bis(2-ethylhexyl) succinate in mixtures with epoxidized soybean oil as bio-based plasticizers for poly(vinylchloride). Polymer Engineering and Science, 2015, 55(3): 634–640
https://doi.org/10.1002/pen.23934
16 Sahoo S K, Mohanty S, Nayak S K. Synthesis and characterization of bio-based epoxy blends from renewable resource based epoxidized soybean oil as reactive diluent. Chinese Journal of Polymer Science, 2015, 33(1): 137–152
https://doi.org/10.1007/s10118-015-1568-4
17 Miao S D, Liu K, Wang P, Su Z G, Zhang S P. Preparation and characterization of epoxidized soybean oil-based paper composite as potential water-resistant materials. Journal of Applied Polymer Science, 2015, 132(10): 41575
https://doi.org/10.1002/app.41575
18 Xiong Z, Dai X Y, Na H N, Tang Z B, Zhang R Y, Zhu J. A toughened pla/nanosilica composite obtained in the presence of epoxidized soybean oil. Journal of Applied Polymer Science, 2015, 132(1): 41220
https://doi.org/10.1002/app.41220
19 Zhang J, Tang J J, Zhang JX. Polyols prepared from ring-opening epoxidized soybean oil by a castor oil-based fatty diol. International Journal of Polymer Science, 2015, 2015 (2015 ): 529235
20 Lathi P S, Mattiasson B. Green approach for the preparation of biodegradable lubricant base stock from epoxidized vegetable oil. Applied Catalysis B: Environmental, 2007, 69(3–4): 207–212
https://doi.org/10.1016/j.apcatb.2006.06.016
21 Chen R Q, Zhang C Q, Kessler M R. Polyols and polyurethanes prepared from epoxidized soybean oil ring-opened by polyhydroxy fatty acids with varying OH numbers. Journal of Applied Polymer Science, 2015, 132(1): 41213
https://doi.org/10.1002/app.41213
22 Karadeniz K, Aki H, Sen M Y, Calikoglu Y. Ring opening of epoxidized soybean oil with compounds containing two different functional groups. Journal of the American Oil Chemists' Society, 2015, 92(5): 725–731
https://doi.org/10.1007/s11746-015-2638-z
23 Liu Z S, Erhan S Z. Ring-opening polymerization of epoxidized soybean oil. Journal of the American Oil Chemists' Society, 2010, 87(4): 437–444
https://doi.org/10.1007/s11746-009-1514-0
24 Huang X J, Liu H, Shang S B, Qi F. Synthesis process of epoxidized dehydrated castor oil. Chemistry and Industry of Forest Products, 2015, 35(4): 41–47
25 Biresaw G, Liu Z S, Erhan S Z. Investigation of the surface properties of polymeric soaps obtained by ring-opening polymerization of epoxidized soybean oil. Journal of Applied Polymer Science, 2008, 108(3): 1976–1985
https://doi.org/10.1002/app.27784
26 Gooch E E. Determination of the iodine value of selected oils: an experiment combining ftir spectroscopy with iodometric titrations. Chemical Educator, 2001, 6(1): 7–9
https://doi.org/10.1007/s00897000438a
27 Gu J, Narang S C, Pearce E M. Curing of epoxy resins with diphenyliodonium salts as thermal initiators. Journal of Applied Polymer Science, 1985, 30(7): 2997–3007
https://doi.org/10.1002/app.1985.070300722
28 Eastoe J, Dalton J S. Dynamic surface tension and adsorption mechanisms of surfactants at the air-water interface. Advances in Colloid and Interface Science, 2000, 85(2–3): 103–144
https://doi.org/10.1016/S0001-8686(99)00017-2
29 Inoue T, Yamakawa H. Micelle formation of nonionic surfactants in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate: Surfactant chain length dependence of the critical micelle concentration. Journal of Colloid and Interface Science, 2011, 356(2): 798–802
https://doi.org/10.1016/j.jcis.2011.01.022
30 Liu Z S, Biresaw G. Synthesis of soybean oil-based polymeric surfactants in supercritical carbon dioxide and investigation of their surface properties. Journal of Agricultural and Food Chemistry, 2011, 59(5): 1909–1917
https://doi.org/10.1021/jf1035614
31 Antonoff G. On the validity of antonoff's rule. Journal of Physical Chemistry, 1942, 46(4): 497–499
https://doi.org/10.1021/j150418a009
32 Van Oss C J. Interracial forces in aqueous media.New York:Marcel Dekker, 2000
33 Voutsas E C, Yakoumis I V, Tassios D P. Prediction of phase equilibria in waterralcoholralkane systems. Fluid Phase Equilibria, 1999, 158–160: 151–163
https://doi.org/10.1016/S0378-3812(99)00131-4
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed