Journal of Oleo Science Copyright ©2012 by Japan Oil Chemists’ Society J. Oleo Sci. 61, (5) 255-266 (2012) Production of Ethoxylated Fatty Acids Derived From Jatropha Non-Edible Oil As a Nonionic Fat-Liquoring Agent Y. El-Shattory1＊ , Ghada A. Abo-ELwafa1, Saadia M. Aly1 and EL -Shahat H. A. Nashy2 1 Fats and Oils Department, National Research Centre, Dokki, Cairo, Egypt. 2 Department of Chemistry of Tanning Materials and Leather Technology, National Research Centre, Dokki, Cairo, Egypt. Abstract: Natural fatty derivatives (oleochemicals) have been used as intermediate materials in several industries replacing the harmful and expensive petrochemicals. Fatty ethoxylates are one of these natural fatty derivatives. In the present work Jatropha fatty acids were derived from the non edible Jatropha oil and used as the fat source precursor. The ethoxylation process was carried out on the derived fatty acids using a conventional cheap catalyst (K2CO3) in order to obtain economically and naturally valuable non- ionic surfactants. Ethoxylation reaction was proceeded using ethylene oxide gas in the presence of 1 or 2% K2CO3 catalyst at 120 and 145°C for 5, 8 and 12 hours. The prepared products were evaluated for their chemical and physical properties as well as its application as non- ionic fat-liquoring agents in leather industry. The obtained results showed that the number of ethylene oxide groups introduced in the fatty acids as well as their EO% increased as the temperature and time of the reaction increased. The highest ethoxylation number was obtained at 145°C for 8 hr. Also, the prepared ethoxylated products were found to be effective fat-liquors with high HLB values giving stable oil in water emulsions. The fat-liquored leather led to an improvement in its mechanical properties such as tensile strength and elongation at break. In addition, a significant enhancement in the texture of the treated leather by the prepared fat-liquors as indicated from the scanning electron microscope (SEM) images was observed. Key words: Jatropha Fatty Acids, Fat-liquor, Ethylene Oxide Gas, Chrome Tanned Leather, Ethoxylated Fatty Acids, Mechanical Properties, Scanning Electron Microscope. 1 INTRODUCTION products2）. Also ethoxylated methyl laureates have been Recently, the world is directed to nature in all aspects of studied as wetting agents3）. life in order to reduce environmental pollution and health Fatty acid ethoxylates and alcohol ethoxylates can be hazards combined with synthetic materials and at the same readily obtained by the direct reaction of fatty acids or time save different energy sources. From this point of view, fatty alcohols that have an active hydrogen in their mole- natural fatty derivatives（oleochemicals）have been used as cules with ethylene oxide in the presence of an alkaline intermediate materials in several industries replacing the （e.g. sodium hydroxide）or an acidic catalyst（e.g. antimony harmful and expensive petrochemicals. pentachloride）4）. Overused edible oils were ethoxylated Fatty ethoxylates are one of these fatty derivatives in using potassium hydroxide catalyst at 180℃ for 20 h5）. which a fatty acid or fatty alcohol is used as the natural Ethylene oxide, however, cannot directly react with fatty precursor in ethoxylates preparation. Ethylene oxide- methyl esters that have no active hydrogen by using those based nonionic surfactants are compounds that contain a catalysts6）. poly（ethylene oxide）chain as a hydrophile1）. Ethoxylated Nowadays, Jatropha tree has been successfully cultivat- fatty acid esters are well known as ether-ester-type non- ed in Egypt as it can grow well in the desert as it withstand ionic surfactants with numerous applications. For example, drought and can be irrigated with treated sewage water ethoxylated stearyl stearates are used as emulsifi ers, dis- since its oil is non-edible. Jatropha seeds contain about persants or oil phase adjusters in cosmetics or in industrial 27-40％ non edible viscous oil which can be used for ＊ Correspondence to: Y. El-Shattory, Fats and Oils Department, National Research Centre, Dokki, Cairo, Egypt. E-mail: [email protected] Accepted November 18, 2011 (recieved for review May 17, 2011) Journal of Oleo Science ISSN 1345-8957 print / ISSN 1347-3352 online http://www.jstage.jst.go.jp/browse/jos/ http://mc.manusriptcentral.com/jjocs 255 Y. El-Shattory, Ghada A. Abo-ELwafa, Saadia M. Aly et al. biodiesel production, manufacture of candles and soap, in 2 EXPERIMENTAL cosmetics industry, paraffin substitute or extender and 2.1 Materials other industial applications. So, this work explores another 2.1.1 Jatropha oil was extracted from Jatropha curcas usage of the non edible Jatropha fatty acids as a fat-liquor- seeds which were cultivated in southern parts of ing agent in order to save the needed edible fats and oils Egypt using commercial n-hexane. for food purposes. 2.1.2 Oil was saponified using potassium hydroxide and Leather is a tanned animal hide or skin. Leather industry free fatty acids were obtained by precipitating the involves the removal of a great part of hide substances like salt using HCL and extracted using light petroleum hair, soluble proteins, epidermis, fat, and fl esh by mechani- ether. cal and chemical processes. Tanning is a durable preserva- 2.1.3 Ethylene oxide gas cylinder was purchased from Eti- tion of perishable biological material, this means that, the co Gas Company for gases（EL-Sharqia for gases, 10th purpose of tanning is to bring irreversible stabilization of of Rmadan Industrial City）. native proteins that is prone to putrefaction and increase 2.1.4 Potassium carbonate catalyst and all solvents and its resistance to enzymatic degradation and chemicals. chemicals used were of highly pure grade purchased Chrome tanned is the most important and common tanning from Merck. agents, which used for the production of all types of leather7, 8）. But chrome tanned leather when dries out, cohesion of the 2.2 Methods fi bers take place resulting to hard intractable leather which 2.2.1 Determination of fatty acid composition: is quite diffi cult to re-hydrate9）. This means that, chrome Fatty acid composition was determined for the separated tanned leather when dries out, it will become bony, hard Jatropha fatty acids as follows: and thus will be unsuitable for use in most purposes, 2.2.1.1 Preparation of fatty acid methyl esters: besides its color turns darker and becomes less appealing. About 0.2 gm of Jatropha fatty acids was mixed with 30 Therefore, fat-liquoring process is an essential operation ml sulfuric acid : methanol（4 : 96 v/v）in a 250 ml round by which an introduction of a fatty matter into the leather bottom fl ask. The contents were then heated under refl ux fi bers takes place. Incorporation of fat-liquor into leather for about three hours. The methyl esters were thrice ex- reduces the damaging effect of air oxidation and control tracted with petroleum ether（40-60℃）then it was washed the differential shrinkage of grain versus corium of the several times with distilled water till the washings were leather during drying process. Therefore, introducing a lu- neutral to phenol phthalein indicator. The combined fatty bricant into the leather keeps the fi bers apart during drying acids methyl esters layers were dried over anhydrous and reduces frictional forces within the fi ber weaves thus sodium sulfate and fi ltered. The petroleum ether was then allowing the fi bers to move laterally over each other. Also, removed using a rotary evaporator and aliquots of the fatty it gains the leather grains specifi c properties which make it acid methyl esters were analyzed by gas chromatogra- suitable for its most effective utilization10）. In addition to phy12）. above fat-liquor helps to prevent the loosening of the 2.2.1.2 Gas-liquid chromatographic analysis of fatty acids leather grain and intended to lubricate the tanned leather methyl esters: fi bers to obtain leather of full and soft handle, abrasion re- The identification of the components of fatty acids sistance, fl exibility, pliability and stretching as well as im- methyl esters was done using gas liquid chromatography proving its mechanical properties11）. on a Hewlett Packard Model 6890 chromatograph equipped The aim of this work is to utilize non-edible vegetable oil under the following conditions: newly cultivated in Egypt like Jatropha oil in the prepara- - Separation was done on an INNO wax（polyethylene tion of ethoxylated fatty acids to be used as nonionic sur- glycol）Model No. 19095 N-123, 240℃ maximum, capil- factants. On this base, the derived Jatropha fatty acids lary column 30.0 m×530 μm×1.0 μm, nominal fl ow 15 were used for the preparation of ethoxylated nonionic sur- ml/min. with average velocity 89 cm/sec. and pressure factant under different reaction conditions and the prod- 8.2 psi. ucts were applied as leather fat-liquors in order to replace - Column temperature was 240℃ with temperature pro- the usage of industrial one with a safe to environment, ef- gramming: Initial temperature 100℃ to 240℃ maximum fective and healthy natural intermediate. The emulsion sta- with 10℃ rising for each minute and then hold at 240℃ bility of the prepared nonionic fat-liquors was evaluated as for ten minutes. well as their application in leather fat-liquoring. Also, the - Injection temperature 280℃, back inlet, with split ratio investigation of the resulting fat-liquored chrome tanned 8:1, split fl ow 120 ml/min., gas saver 20 ml/min. leather was taken into consideration. -Carrier gas was nitrogen with fl ow rate 15 ml/min. -Flame ionization detector temperature 280℃. -Hydrogen fl ow rate 30 ml/min. -Air fl ow rate 300 ml/min. 256 J. Oleo Sci. 61, (5) 255-266 (2012) Production of Ethoxylated Fatty Acids Derived From Jatropha Non-Edible Oil As a Nonionic Fat-Liquoring Agent 2.2.2 Ethoxylation reaction 2.2.3.3 FT-IR Analysis The reaction of fatty acids with ethylene oxide was The change in the functional groups of fatty acids before carried out in the closed system shown in Fig.