Production of Ethoxylated Fatty Acids Derived from Jatropha Non-Edible Oil As a Nonionic Fat-Liquoring Agent Y

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 nonionic 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 nonionic 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. 1 according and after ethoxylation was studied using FT-IR analysis. All to Wrigley et. al.13）. Jatropha fatty acids（5 gm）and 1％（or control and ethoxylated samples were subjected to FT-IR

2％）potassium carbonate（K2CO3）as catalyst were mixed in analysis on a Nexus 670 Fourier Transform Infra Red spec- the round flask of the system. The reaction mixture was trometer, Thermo Nicolet, USA. The FT-IR spectra were stirred using a magnetic stirrer and heated under nitrogen analyzed using“ Omnic 5.2a” software. A fixed sample atmosphere to the desired reaction temperature（120 and volume（5μl）of each sample was carefully and homoge- 145℃）. neously spread between two KBr disks of fixed weights. The gentle fl ow of nitrogen was then halted and the ni- The samples were referenced to their own blank KBr disks. trogen was replaced by ethylene oxide which was thereaf- For collection of the data, a DTGS detector and KBr beam- ter kept in harmony with the rate of the reaction. The fl ow splitter were used. of ethylene oxide was stopped and replaced by nitrogen to 2.2.3.4 Quantitative determination of the ethoxylated cool the reaction mixture after the required period of time products （5, 8, 12 h）. The weight difference of the ethoxylation The ethoxylated products were quantitatively deter- system before and after the reaction was recorded. mined through: 2.2.3 Evaluation of the ethoxylated Jatropha fatty acids 2.2.3.4.1 Molecular weight determination using Gel Perme- The prepared ethoxylated samples were then evaluated ation Chromatograph（GPC） by the following analysis: The average molecular weight of Jatropha fatty acids 2.2.3.1 Chemical Characteristics before and after ethoxylation were determined using gel 2.2.3.1.1 Determination of iodine value（I.V.）, acid value permeation chromatograph（GPC）coupled with RI detector. （A.V.）and saponifi cation value（S.V.）: Samples were dissolved in tetrahydrofuran and the GPC They were carried out according to AOCS Official instrument used in the measurements was a modified Methods Cd 3d-63, Cc 18-80 and Tl 1a-6414）respectively. HPLC, Waters 600 System Controller, 717 plus Autosam- 2.2.3.2 Physical characteristics pler. Columns: Phenomenex Phenogel 10 um 500 A, 250× 2.2.3.2.1 Determination of the solubility of ethoxylated 8 mm Phenomenex Phenogel 5 um 50 A, 300×7.8 mm. De- samples in different solvents: tection: Waters model 2410 Refractive index, ATTN＝16x. The solubility of ethoxylated samples was determined in Eluent: dimethylformamide DMF（100％ by vol）. Flow rate: water, oil, ethanol, n-hexane and diethyl ether at room 0.7 ml/min. Temperature: 50℃. Injection volume: 25ul. temperature and at 75℃ or at the boiling point of the 2.2.3.4.2 Degree of Ethoxylation solvent13）. The degree of ethoxylation was calculated depending on 2.2.3.2.2 Melting point determination the determination of the introduced number of ethylene The melting point of the ethoxylated samples was re- oxide as follows: corded using electro thermal IA 9100 digital melting point 1） The number of ethylene oxide（n）moles introduced in apparatus. the fatty acids was estimated depending on the molecular weight difference of the sample before and after ethoxylation. 2） The degree of ethoxylation was calculated by dividing the molecular weight of the group’s number of ethylene oxide added by the total molecular weight of the ethoxylated sample multiplied by 100, equation 1. nx44 EO％＝ ×100 （1） R＋（nx44） Where n＝Number of ethylene oxide moles. 44＝Molecular weight of one mole ethylene oxide. R＝ Molecular weight of the hydrophobe（fatty acid frac- tion）. 2.2.3.5 Hydrophile-Lipophile Balance（HLB） Hydrophile-lipophile balance of the nonionic fat-liquors was calculated based on equation（2）15）. EO ％ HLB＝（2） 5 Fig. 1 Apparatus used for the reaction with ethylene Where EO％: is the percent of introduced ethylene oxide oxide.

257 J. Oleo Sci. 61, (5) 255-266 (2012) Y. El-Shattory, Ghada A. Abo-ELwafa, Saadia M. Aly et al.

2.2.4 Fat-Liquoring Process 3 RESULTS AND DISCUSSION The leather samples were worked up in wet-finishing 3.1 Fatty acid composition process as follow: Table 1 shows fatty acid composition of Jatropha fatty The leather pieces were first washed with water for acids. Fatty acids content can be divided into two main about 15 minutes and drained water off. Then neutraliza- groups as illustrated in Table 1. tion process was carried out using 1％ sodium formate and It can be seen that, the saturated fatty acids content of running the drum at ≈ 10 rpm for 15 minutes at ambient Jatropha fatty acid was（19.18％）while unsaturated fatty temperature. Thereafter, 0.5％ sodium bicarbonate was acids content was（81.21％）. Also, it was noticed that, the added and the drum was run for additional 10 min at the ratio of total saturated fatty acids to the total unsaturated same speed. The leather pieces gave a greenish blue color fatty acids（1: 4.23）. Oleic acid constitutes more than 61％ with bromo cresol green throughout the whole thickness of the total unsaturated fatty acids, while linoleic acid had （pH 5.0-5.3）. The neutralized leather pieces were retanned much higher value（34％）than linolenic（2％）of the total and dyed with 5％ acid dye for 30 minutes. Then, the fat- unsaturated fatty acids. On the other hand, palmitic acid emulsion was added to the dyeing bath at room tempera- showed more than 83％ of the saturated fatty acids and ture. After complete addition of the fat liquor, the drum 15％ of the total fatty acids. was run at ≈ 10 rpm for 40 minutes at 30℃. The leather pieces were washed with water for about 10 minutes, 3.2 Ethoxylation Reaction removed from the drum, sammed and left to dry in air The ethoxylation reaction had failed when it was carried through hanging up at room temperature. The dried out directly on Jatropha oil at different temperatures

leather pieces were used for the various physical proper- （80-180℃）and different percentages of K2CO3 catalyst. ties investigations. This can be attributed to the triglyceridic composition - All percentages and chemical additives doses were cal- （esters）of Jatropha oil which cannot be ethoxylated using

culated on the basis of leather weight（w/w）. conventional catalysts like K2CO3 due to lack of the active 2.2.5 Mechanical Measurements hydrogen necessary to initiate such reaction using these Dumbbell shaped specimens 50 mm length and 4 mm catalysts1）. Therefore, free fatty acids were separated from （neck width）were used for measurements of mechanical the oil to enhance the reaction using the cheap and avail-

properties（tensile strength and elongation at break）. The able catalyst K2CO3 as illustrated in Scheme 1. measured data are the average of four transverse and lon- This reaction would lead only to the formation of mono- gitudinal measurements for each sample. These tests were esters17）which means that the reaction with ethylene oxide carried out using an Instron Machine（model 1195）16）. The would be preferred towards esteriﬁ cation reaction. cross-head speed was controlled at 50 mm/min and the It is worthy mentioned here that, when the reaction was

tests were done at room temperature（25℃）. carried out at 80-120℃ using 1％ K2CO3 no product was 2.2.6 Scanning Electron Microscope obtained. But, ethoxylated product was obtained at 145℃

Specimens of experimental and control were prepared using 1％ K2CO3 and/or at 120℃ using 2％ K2CO3. as circular samples（10 mm）and then subjected to sputter coating of gold ions to prepare a conducting medium 3.3 Evaluation of the ethoxylated Jatropha fatty acids （sputter coater-Edwards-Model S-150 A, Eng）. A Jeol 3.3.1 Chemical Characteristics scanning microscope（Japan）JSM-T20 was used for the mi- Table 2 shows the chemical characteristics of the ethox-

croscopic study. ylated Jatropha fatty acids at 145℃ using 1％ K2CO3 for different periods of time. It is clear from Table 2 that ethoxylation reaction caused a large decrease in acid value due to a large consumption of the fatty acids as ethoxylation reaction mainly happens with the free carboxylic groups. Also, a large decrease in

Table 1 Fatty acid composition of Jatropha fatty acids. Fatty acids, % Saturated Unsaturated

Fatty acids C14 C16 C20 C22 C16:1 C18:1 C18:2 C18:3 of Jatropha Myristic Palmitic Arachidic Behenic Total Palmitoleic Oleic Linoleic Linolenic Total oil acid acid acid acid acid acid acid acid Percents, % 0.93 15.93 1.41 0.91 19.18 1.21 50.20 28.18 1.62 81.21

258 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

Scheme 1 The reaction of ethylene oxide with fatty acids using alkaline catalyst.

Table 2 Chemical Characteristics of Jatropha fatty acids ethoxylated

at145℃ using 1% K2CO3 as a catalyst for different periods of time. Saponifi cation Time of reaction Acid value (mg Iodine value Value (hours) KOH/g) (g/100g) (mg KOH/g) 0* 194.01 111.42 190.46 5 0.35 29.76 52.36 8 0.22 16.31 18.22 12 0.30 10.95 17.33 ・Control sample (non ethoxylated Jatropha fatty acids). iodine value was observed which indicates a relative reduc- obtained after 5 h, while the reaction started after 8 hours. tion in the magnitude of the unsaturated moiety to the mo- This is might be due to that during the early stage of fatty lecular weight of the product after ethoxylation reaction. acid ethoxylation there is a period of time where negligible In addition to a large decrease in saponification value amounts of product are formed which is called the induc- due to the blockage of the saponifi able carboxylic groups tion period. After this initial period, reaction rate increases. of the fatty acids during the ethoxylation reaction. As the Therefore, the reaction was started after fi ve hours when it temperature and time of the ethoxylation reaction in- was carried out at 145℃ and in the 8th hour at 120℃ creased the acid, iodine and saponification values were which agreed with results obtained by O'Lenick and Par- found to decrease. kinson18）. Acid, iodine and saponifi cation values were also Table 3 represents the chemical characteristics of the found to decrease during the reaction at 120℃. ethoxylated fatty acids prepared at120℃. It is clear from 3.3.2 Physical Characteristics Table 3 that ethoxylating Jatropha fatty acids at 120℃ was 3.3.2.1 Melting point carried out using 2％ K2CO3 because 1％ did not facilitate The appearance of the samples differed before and after the reaction. the reaction. It was observed practically that as the tem- Also, it could be noticed from Table 3 that no-product perature and time of the reaction increased the liquid fatty

259 J. Oleo Sci. 61, (5) 255-266 (2012) Y. El-Shattory, Ghada A. Abo-ELwafa, Saadia M. Aly et al.

Table 3 Chemical Characteristics of Jatropha fatty acids ethoxylated

at120℃ using 2% K2CO3 for different periods of time. Saponiﬁ cation Time of reaction Acid value (mg Iodine value Value (hours) KOH/g) (g/100g) (mg KOH/g) 0* 194.01 111.42 190.46 5 No product No product No product 8 0.24 72.30 138.88 12 0.22 14.62 36.64 ・Control sample (non ethoxylated Jatropha fatty acids).

Table 4 Melting point versus iodine value of Jatro- Table 5 Melting point of Jatropha fatty acids ethox-

pha fatty acids ethoxylated at145℃ using ylated at120℃ using 2% K2CO3 for differ-

1% K2CO3 for different periods of time. ent periods of time. Melting point Melting point Time of reaction of Ethoxylated Iodine value Time of reaction of Ethoxylated Iodine value (hours) Jatropha F.A. (g/100g) (hours) Jatropha F.A. (g/100g) (℃) (℃) 5 31.9 29.76 8 liquid 72.30 8 52.7 16.31 12 44.0 14.62 12 57.2 10.95

Table 6 Solubility of ethoxylated Jatropha fatty acids at 120 and 145℃ for different periods of time. Solubility in different solvents at different temperatures Solvent Temp. Ethoxylated Jatropha fatty acids at 120℃ at 145℃ 5 hr 8 hr 12 hr 5 hr 8 hr 12hr Room Temp. － SS S S PS S Water 75℃－SSSSSS － Room Temp. － S PSPSPSPS Vegetable 75℃－SSSSS Oil － Room Temp. － SSSSPS Ethanol 75℃－SSSSS － Room Temp. － S SS S SS I Diethyl Boiling point － SSSPSI ether － n - Room Temp. － SSSPSSSI hexane Boiling point － S SS S PS I Where: S＝soluble PS＝Partially soluble SS＝Sparingly soluble I＝Insoluble

260 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

Fig. 2 FT-IR chart of polyethoxylated oleic acid (9 mole ethylene oxide). Fig. 3 FT-IR chart of Jatropha fatty acids acid at room temperature turned after ethoxylation to be solid at room temperature. Tables 4 and 5 show that the melting points of the ethoxylated fatty acids samples increased as the time and temperature of the reaction increased. This can be attributed to the relative decrease in the magnitude of unsaturation moiety related to the product molecular weight during the reaction. 3.3.2.2 Solubility in different solvents: Table 6 shows that, almost all of the ethoxylated Jatro- pha fatty acids samples prepared at 145℃ were soluble in water either at room temperature or at 75℃. Ethoxylated Jatropha fatty acids prepared at 120℃ for 12hr was found to be soluble in water. All of the prepared samples were Fig. 4 FT-IR chart of ethoxylated Jatropha fatty acids soluble in warm vegetable oil and warm ethanol. As the at 145℃ using 1% K CO for 5 hours. temperature and time of ethoxylation reaction increased 2 3 the solubility of the samples in diethyl ether or n-hexane decreased. 3.3.3 FT-IR Analysis Figure 2 shows an FT-IR chart of polyethoxylated oleic acid（9 mol ethylene oxide）as a reference spectrum19）. The FT-IR spectra of Jatropha fatty acids before and after ethoxylation were shown in Figs. 3-8. The spectra comparison revealed that, a broad characteristic absorption band appeared at about 3430 cm－1 for O-H stretching vi- bration intermolecular hydrogen bonded due to the ethoxylated product. This band was found to be more broad and strong at 145℃ for 8hr, at 145℃ for 12hr and at 120℃ for 12hr. The absorption band at ～3005 cm－1 representing Fig. 5 FT-IR chart of ethoxylated Jatropha fatty acids the unsaturation moiety in the fatty acid sample disap- at 145 using 1% K CO for 8 hours. peared after ethoxylation. Two bands at positions ～2925 ℃ 2 3 and ～2855 cm－（1 C-H stretching）in samples before ethoxylation（Fig. 3）became sharper after ethoxylation this may 3.3.4 Quantitative Determination of Ethoxylated products be due to the increase in the number of CH2 groups. A （Determining the number of introduced ethylene ox- band at ～1177 cm－1 appeared after ethoxylation which ide moles）. represents C-O-C group. The number of ethylene oxide moles（n）was determined Generally, the bands were more strong and detectable depending on the highest increase in weight of sample for samples prepared at 145℃ than those prepared at after ethoxylation as follows: 120℃. The previously mentioned ethoxylated family bands 3.3.4.1 Weight difference determination were agreed with that recorded by Fiveash Data Manage- Table 7 illustrates the weight increase of the ethoxylated ment19）and by Ovalles et al.20）. sample. Depending on the highest increase in weight（Table

261 J. Oleo Sci. 61, (5) 255-266 (2012) Y. El-Shattory, Ghada A. Abo-ELwafa, Saadia M. Aly et al.

Fig. 8 FT-IR chart of ethoxylated Jatropha fatty acids

at 120℃ using 2% K2CO3 for 12hours.

Table 7 Weight difference of Jatropha fatty acids Fig. 6 FT-IR chart of ethoxylated Jatropha fatty acids before and after ethoxylation at 120 and at 145℃ using 1% K2CO3 for 12 hours. 145℃ for different periods of time.

K2CO3 Reaction Time of Increase in catalyst % temperature reaction weight (gm) 5 hours 0.00 2% 120℃ 8 hours 2.75 12 hours 15.2 5 hours 13.80 1% 145℃ 8 hours 23.4 12 hours 23.5

creased after ethoxylation by more than three times than Fig. 7 FT-IR chart of ethoxylated Jatropha fatty acids that of fatty acids, due to the introduction of high number at 120 using 2% K CO for 8 hours. ℃ 2 3 of ethylene oxide molecules into the fatty acids. Further- more, it was noticed that the average molecular weight of 7）, two ethoxylated samples were selected to be analysed ethoxylated Jatropha fatty acids increase as the reaction for their molecular weight determination temperature increases. 3.3.4.2 GPC Molecular weight and quantitative determina- 3.3.4.3 Ethoxylation percent（EO％）and Hydrophile-lipo- tion phile balance（HLB） The number and weight-average molecular weights（Mns, The number of ethylene oxide moles and their percent Mws）of Jatropha fatty acids before and after ethoxylation （EO％）introduced into ethoxylated Jatropha fatty acids as are shown in Table 8. well as hydrophile-lipophile balance（HLB）were calculated As illustrated in Table 8, the molecular weight highly in- based on the difference in molecular weight of Jatropha

Table 8 Mn, Mw and PDI of ethoxylated Jatropha fatty acids. Samples Mn , g/mol Mw , g/mol PDI(Mw/ Mn) Jatropha fatty acids 4.0244×102 5.1871×102 1.2889×102 Ethoxylated Jatropha fatty acids at 120℃ for 12 hr using 1.4098×103 2.5812×103 1.8309×103

2% K2CO3 catalyst Ethoxylated Jatropha fatty acids at 145℃ for 8 hr using 2.3544×103 4.4202×103 1.8774×103

1% K2CO3 catalyst Where: Mn, number average of molecular weight, Mw, weight average of molecular weight, PDI, poly dispersity

262 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

Table 9 Effect of ethoxylation on Jatropha fatty acids and their EO% and HLB values after ethoxylation. Moles number of Molecular Sample type ethylene oxide EO%* HLB* weight introduced Jatropha fatty acids 518.71 －－－ Ethoxylated Jatropha fatty acids at 120℃ for 12 hr using 2581.2 46.88 79.9 15.98

2% K2CO3 catalyst Ethoxylated Jatropha fatty acids at 145℃ for 8hr using 4420.2 88.67 88.27 17.65

1% K2CO3 catalyst * EO% = (Difference in molecular weight / molecular weight of ethoxylated Jatropha fatty acids)*100 * HLB = EO%/5

fatty acids before and after ethoxylation. The selected eth- Table 10 Mechanical properties of leather treated with oxylation conditions enhanced the introduction of a high two ethoxylated Jatropha fatty acids fatliquors. number of ethylene oxide groups and consequently in- Tensile Strength, Strain at crease in EO％ as shown in（Table 9）. M. Pa rupture, % The Hydrophile-lipophile balance（HLB）concept is one of the most important factors in the evaluation of a fat-li- Chrome tanned leather 20.15 71.2 quor emulsion. HLB is an expression of the relative simul- Fatliquored leather (1) 29.6 132.5 taneous attraction of a surfactant for water and/or for oil 120℃/12 hr 2% K2CO3 （or for the two phases）, this mean that HLB of a surfactant Fatliquored leather (2) determines the emulsion type that tend to be formed21）. 32.9 140.25 145℃/ 8 hr 1% K2CO3 Akoh and Nwosu22）found that low value HLB of 3-6 will promote or stabilize W/O emulsions, while an intermediate values（8-13）will stabilize O/W emulsions, and high values out on neutralized leather using 6％/100 g leather. Me- such as（15-18）will act as a solubilizier15）. chanical properties include the measurement of the tensile If the fat-liquor is unstable, it cannot give a proper fat-li- strength and elongation at break, have been given in the quoring effect, due to the separation of fat from the emul- greatest consideration on the evaluation of fat-liquored sion before it's fi xing to the leather fi ber. So that, it is nec- leather, because, it gives an indication of fi ber lubricity. It essary to evaluate the stabilization of prepared non-ionic is obvious from Table 10 that tensile strength and elonga- fat-liquors emulsions through determining HLB value. tion at break of fat-liquored leather were improved than The prepared ethoxylated Jatropha fatty acids at 120℃ that of the un fat-liquored chrome tanned one. Also, it was

for 12 hr using 2％ K2CO3 catalyst have HLB value of 15.98 noticed from Table 10 that, mechanical properties of while it was found to be 17.65 for the sample ethoxylated leather treated by ethoxylated Jatropha fatty acids at

at 145℃ for 8 hr using 1％ K2CO3 catalyst（Table 9）. This 145℃ for 8 hr using 1％ K2CO3 catalyst as a fat-liquor was means that, they forms an“ O/W” emulsion type, and relatively higher than that of ethoxylated Jatropha fatty

simply dispersible in water. In other words a fineness of acids at 120℃ for 12 hr using 2％ K2CO3 catalyst. The en- emulsion is formed since ethoxylated portions as well as hancement of mechanical properties is attributed to good non-ethoxylated portion of the ester, which is present in lubrication of fi bers, as confi rmed by scanning electron mi- the fat-liquor, are emulsifi able. The obtained HLB indicated crograph, Figs. 9, 10. that the prepared ethoxylated Jatropha fatty acids can 3.3.6 Scanning Electron Microscopy（SEM） form a stable emulsion and transfer from the aqueous bath The most effi cient tool for the evaluation of fat-liquored to the leather and penetrate into it, which means that they leather is the Scanning Electron Micrograph（SEM）because can be used as good fat-liquors. it looks deeply into hide fiber structure, and shows the 3.3.5 Mechanical Characters of fat-liquored leather effect of fat-liquor on fiber and grain surface. It was ob- The mechanical properties were evaluated according to served from microscopically analyses（SEM）that, the standard Egyptian physical testing method of leather treated leather by the prepared fat-liquors has a smooth （ES-123）23）, Table 10. Fat-liquoring process was carried fi bers and soft grain, and modifi ed handle because the pre-

263 J. Oleo Sci. 61, (5) 255-266 (2012) Y. El-Shattory, Ghada A. Abo-ELwafa, Saadia M. Aly et al.

Fig. 9a SEM of grain surface of chrome tanned leather. Fig. 10a SEM of ﬁ ber bundles of chrome tanned leather.

Fig. 9b SEM of grain surface of chrome tanned leather Fig. 10b SEM of ﬁ ber bundles of chrome tanned leath- fat-liquored by ethoxylated Jatropha fatty acids er fat-liquored by ethoxylated Jatropha fatty

at 120℃ for 12 hr using 2% K2CO3catalyst. acids at 120℃ for 12 hr using 2% K2CO3 catalyst.

Fig. 9c SEM of grain surface of chrome tanned Fat- Fig. 10c SEM of fiber bundles of chrome tanned liquored by ethoxylated Jatropha fatty acids at leather fat-liquored by ethoxylated Jatropha

145℃ for 8 hr using 1% K2CO3catalyst. fatty acids at 145℃ for 8 hr using 1% K2CO3 catalyst.

264 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

pared fat-liquors protect the surface of the fibers with a 2） Nakamura, H. I.; Hama, I.; Fujimori, Y. Jpn. Pat., thin film of lubricant resulting soft leather, Figs. 9, 10. JP4-279552（1991）. Scanning electron microscope of the cross-section of the 3） Weil, J. K.; Koos, R. E.; Linfield, W. M.; Parris, N. J. leather fi bers before（Fig. 10a）and after fat-liquoring（Fig. Am. Oil Chem. Soc., 56, 873（1979）. 10b & c）showed a signifi cant lubrication of fi ber bundles 4） Schick, M. J. Nonionic surfactants, Marcel Dekker, and surface grain of fi ne and loose texture. New York（1966）. In addition, the grain surface（x50）of the treated leather 5） Nashy, E. H. A.; Abo-Elwafa, G. A. Highly Stable Non- exhibits no cracking（fi rm grain）and no fat-spew, Fig. 9 b, c. Ionic Fat-Liquors Based on Ethoxylated Overused This can be attributed to the low percentage of free fatty Vegetable Oils, Accepted for publication in J. Am. Oil acids in the prepared fat-liquors, where, high free acid Chem. Soc., 08 March（2011）. tends to cause spewing and leads the production of narsh 6） Hama, I.; Okamoto, T.; Nakamura, T. Preparation and and cracky leather. Also, the vivid shade of the fat-liquored properties of ethoxylated fatty methyl ester nonionics, leather was obtained i.e., the treated leather has a uniform J. Am. Oil Chem. Soc., 72, 781-784（1995）. shade. This is due to that the prepared fat-liquor has a 7） Richard, S. Makdisi Tannery wastes defi nition, risk as- lower iodine value, Tables 2 & 3. Iodine value has a great sessment and clean up options, Berkeley, California. J. effect on color shade, where higher iodine value indicate of hazardous materials 29:1, 79-96（1991）. that the fat-liquor will give yellow eventually when applied 8） Alexander, K.; Donahue, V. Cleaner technologies in the to white leathers due to light（UV. light）and temperature tanning industry. EPA environmental challenge of the may breakdown the unsaturation moiety（neutral fat）into 1990’s. International conference on pollution preven- acids［23］, leading to fat-spews as well as possible fogging, tion: clean technologies and clean products pp 19-31, resulting in yellowing and the production of bad odors. The 10-13 June（1990）. yellowing of fat-liquors interferes especially with light 9） Burgess, D. General aspects of fat-liquoring: An intro- shades. duction to the application and chemistry of fat liquoring. J. soc. Leather Techno. & chemists 78, 39-43 （1993）. 10） Alexander, K. T. W.; Convington, A. D.; Stosic. R. G. CONCLUSIONS The production of soft leather: Part 2. Drying and The results of this work revealed that:- stress softening. JALCA 88, 254-269（1993）. 1． Ethoxylation reaction was carried out under different 11） Heidemann, E. Fundamentals of leather manufactur- conditions and the optimum conditions were found ing. Eduard Roether KG, Darmstadt, Chapter 15, ISBN

to be at 145℃/8hr,1％ K2CO3 & 120℃/ 12hr, 2％ 3-7929-0206-0（1993）.

K2CO3 with a high number of introduced ethylene 12） Ludde, F. E.; Barvord. R. A. Reimenschnider. R. W. Di- oxide groups. rect conversion of lipid components to their fatty acid 2． The prepared ethoxylated fat-liquors at 145℃/8hr, 1％ methyl esters. J. Am. Oil Chem. Soc., 73, 447-451

K2CO3 have superior properties of better penetration （1960）.

in the leather than at 120℃/ 12hr, 2％ K2CO3 due to 13） Wrigley, A. N.; Smith. F. D.; Stirton, A. J. Synthetic de- its HLB value. tergents from animal fats. VIII. The Ethenoxylation of 3． Tensile strength and elongation at break as well as fatty acids and alcohols. J. Am. Oil Chem. Soc., 34, texture of leather were markedly improved as the in- 39-43（1957）. troduction of fat-liquors. 14） AOCS Offi cial Method Cd 3d-63, Cc 18-80 and Tl la-64. 4． The prepared ethoxylated fat-liquors based on Official Methods and Recommended Practices of the derived fatty acids has suitability to a far extent for American Oil Chemists’ Society, AOCS, Champaign, IL fat-liquoring of chrome tanned leather. （1996）. 5． Its recommended here that the Egyptian tanner can 15） Fujimoto, T. New introduction to surface active agents, easily reach the fi gure required in the local specifi ca- Sanyo Chemical Industries Ltd. Japan part 3, Chapter tions for such type of leather. 3（187-218）（1985）. 16） Stevenson, W. T. K.; Sefton, M. V. The equilibrium water content of some thermoplastic hydroxyalkyl meth- acrylate polymers J Appl Polym Sci 36（7）, 1541-1553 References （1988）. 1） Cox, M. F. Ethylene oxide-derived surfactants: Pro- 17） Schwartz, A. M.; Perry, J. W. Surface active agents ceedings of the 3rd world conference on detergents: their chemistry and technology, p. 207, Interscience Global perspectives, edited by Arno Cahn, 141-146, publishers, New York（1949）. （1994） 18） O'Lenick, A. J.; Parkinson, J. K. A comparison of the

265 J. Oleo Sci. 61, (5) 255-266 (2012) Y. El-Shattory, Ghada A. Abo-ELwafa, Saadia M. Aly et al.

ethoxylation of fatty alcohol, fatty acid and dimethi- York, London, Sedny（1965）. conol, J. Am. Oil Chem. Soc. 73（1）, 63-66（1996）. 22） Akoh, C. C.; Nwosu, C. V. Emulsifi cation properties of 19） Fiveash Data Management, Inc. FDM FT-IR Spectra polyesters and sucrose ester blends II: Alkyl glycoside Library of Surfactants（1997）. polyesters. J. Am. Oil Chem. Soc. 69（1）, 14-19 20） Ovalles, C.; Bolivar. R.; Cotte. E.; Aular, W.; Carrasquel, （1992）. J.; Lujano, E. Novel ethoxylated surfactants from low- 23） Egyptian Standard Specifi cations Physical methods of value refi nery feedstocks, Fuel 80, 575-582（2001）. leather, E. S 123（1986）. 21） Griffi n, M. C. Emulsions in: Encyclopedia of chemical 24） Selvarangan, R.; Vijayalakshmi, K.; Raghunatha, R. A. technology 8, 117-154, interscience publishers, New O. D. Leather Science 22, 265-276（1975）.

266 J. Oleo Sci. 61, (5) 255-266 (2012)