Synthesis and characterization of castor oil-based polymeric surfactants

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 (g_cmc) 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

References

[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

[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

[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

[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

[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

[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

[7] Ogunniyi D S. Castor oil: vital industrial raw material. Bioresource Technology, 2006, 97(9): 1086–1091

[8] Guner F S. Castor oil dehydration kinetics. Journal of the American Oil Chemists' Society, 1997, 74(4): 409–412

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[31] Antonoff G. On the validity of antonoff's rule. Journal of Physical Chemistry, 1942, 46(4): 497–499

[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

[34] Jasper J J. The surface tension of pure liquid compounds. Journal of Physical and Chemical Reference Data, 1972, 1(4): 841

Acknowledgments

The authors express their gratitude for the financial support provided by the Natural Science Foundation of Jiangsu Province of China (BK2012063, BK20140973) and the National Natural Science Foundation of China (31200446).

Xujuan Huang, He Liu, Shibin Shang, Zhaosheng Cai, Jie Song, and Zhanqian Song declare that they have no conflict of interest or financial conflicts to disclose.

This article does not contain any studies with human or animal subjects performed by any of the authors.

RIGHTS & PERMISSIONS

Higher Education Press and Springer-Verlag Berlin Heidelberg