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Epoxidation of Soybean Oil and Jatropha Oil
Abstract
Soybean oil and jatropha oil have high contents of unsaturated fatty acids which can be converted to epoxy fatty acids. The vegetable oil-based epoxy materials are sustainable, renewable and biodegradable materials replacing petrochemical-based epoxy materials in some applications. To produce epoxidized soybean oil (ESO) and epoxidized jatropha oil (EJO), the epoxidation was carried out by conventional chemistry at 50 o C and atmospheric pressure for about 10 h. The maximum reaction conversion was 83.3% for the epoxidation of soybean oil and 87.4% for the epoxidation of jatropha oil. An excess amount of hydrogen peroxide was necessary in the reaction to achieve high reaction conversion. A possibly undesirable side reaction was reaction of the epoxy ring opening resulting in hydroxy functional groups observed by Fourier Transform Infrared Spectroscopy (FTIR). The highest epoxy content of ESO produced had 6.13% (wt), which is comparable to the commercially available ESO. The highest epoxy content of EJO produced was 4.75% (wt); however, there is no commercially available EJO to make a comparison. This project hopes to help Thailand to start producing vegetable oil-based epoxy ourselves. Moreover, it could give an alternative market to jatropha oil farmers.
... In some studies, the use of a catalyst is even eliminated, but the more concentrated hydrogen peroxide has to be employed together with a higher loading of formic acid [13,14]. Meyer and co-workers [15] reported that epoxidised jatropha oil (EJO) could achieve an OOC of up to 4.75% at a reaction temperature of 50 °C and 10 h of reaction time. By increasing the reaction temperature to 65 °C, the reaction time can be reduced to 5 h with OOC reduced to 4.3% [15]. ...
... Meyer and co-workers [15] reported that epoxidised jatropha oil (EJO) could achieve an OOC of up to 4.75% at a reaction temperature of 50 °C and 10 h of reaction time. By increasing the reaction temperature to 65 °C, the reaction time can be reduced to 5 h with OOC reduced to 4.3% [15]. ...
... In some studies, the use of a catalyst is even eliminated, but the more concentrated hydrogen peroxide has to be employed together with a higher loading of formic acid [13,14]. Meyer and co-workers [15] reported that epoxidised jatropha oil (EJO) could achieve an OOC of up to 4.75% at a reaction temperature of 50 • C and 10 h of reaction time. By increasing the reaction temperature to 65 • C, the reaction time can be reduced to 5 h with OOC reduced to 4.3% [15]. ...
A low cost, abundant, and renewable vegetable oil source has been gaining increasing attention due to its potential to be chemically modified to polyol and thence to become an alternative replacement for the petroleum-based polyol in polyurethane production. In this study, jatropha oil-based polyol (JOL) was synthesised from non-edible jatropha oil by a two steps process, namely epoxidation and oxirane ring opening. In the first step, the effect of the reaction temperature, the molar ratio of the oil double bond to formic acid, and the reaction time on the oxirane oxygen content (OOC) of the epoxidised jatropha oil (EJO) were investigated. It was found that 4.3% OOC could be achieved with a molar ratio of 1:0.6, a reaction temperature of 60C, and 4 h of reaction. Consequently, a series of polyols with hydroxyl numbers in the range of 138-217 mgKOH/g were produced by oxirane ring opening of EJOs, and the physicochemical and rheological properties were studied. Both the EJOs and the JOLs are liquid and have a number average molecular weight (Mn) in the range of 834 to 1457 g/mol and 1349 to 2129 g/mol, respectively. The JOLs exhibited Newtonian behaviour, with a low viscosity of 430-970 mPas. Finally, the JOL with a hydroxyl number of 161 mgKOH/g was further used to synthesise aqueous polyurethane dispersion, and the urethane formation was successfully monitored by Fourier Transform Infrared (FTIR).
... However, oxidation can be reduced by functionalization of the oil at the location of double bonds to form epoxide groups via an epoxidation process. [11] Epoxidation can be carried out in a number of ways that include the conventional chemical treatment, using acid ion exchange resins (AIER), using enzymes, or using metal catalyst. Among all methods listed, the chemical conversion process is the most preferred one. ...
... Properties of Vegetable Oil[10][11] ...
Vegetable oils are most versatile substitutes for other exhaustive hydrocarbon compounds for production of epoxides. Most vegetable oils have high content of unsaturated bond and can be converted into epoxidized fatty acids. These days, epoxidized vegetable oils are great concern as they are obtained from sustainable, renewable natural resources and are environmental friendly. Epoxidation of vegetable oils on an industrial scale is most frequently carried out with peroxyacetic and peroxyformic acids, the products being used as PVC plasticizers. Typical conversions of double bonds to epoxy groups are about 90%. The present paper is review work on various methods and literature survey of epoxidation of vegetable oil.
... Furthermore, Hazmi et al. (2013) reported that the produced EJO had an OOC value of 3.67 % to 3.89 %. Another example of epoxidation reaction was mentioned by Meyer et al. (2008). The OOC value achieved was 4.75 %, and the time taken was about 10 h. ...
... Although it had a higher OOC value, the time taken was prolonged. The OOC value recorded in this work is on par with previous research as it was able to achieve an OOC value of 4.23 % with a shorter time of up to 5 h (Hazmi et al., 2013;Meyer et al., 2008). ...
Bio-based polymer is a promising candidate to substitute conventional petroleum-derived polymer as it is sustainably produced from renewable resources, which helps reduce the production process’ carbon footprint. It also helps reduces humankind’s dependability on fossil fuel-based feedstock. In this work, a sustainable jatropha oil-based polyurethane acrylate (PUA) was successfully prepared and synthesised using a 3-steps process; epoxidation (formation of an epoxy group), hydroxylation (addition of–OH group to opened ring), and acrylation (addition of acrylate group into polyol). The yellowish PUA prepared has a gel consistency, which is sticky and slightly runny. The PUA was characterised by using wet chemical tests such as oxirane oxygen content (OOC), acid value (AV), hydroxyl number (OHV) and iodine value. OOC value for the PUA synthesised was 4.23 % at the 5 hr reaction time. At the same time, the Epoxidised jatropha oil (EJO) used to prepare polyol records a hydroxyl number of hydroxyl 185.81 mg KOH/g and an acid value of 1.06. The polyol prepared was mixed with 2, 4-toluene-diisocyanate (TDI) and Hydroetyhlmethacrylate (HEMA) to produce PUA. The PUA was characterised by thermogravimetry analysis (TGA) and electrochemical impedance spectroscopy (EIS). TGA analysis shows that the polymer is stable up to 373 K, whereas the EIS analysis records an ionic conductivity of (5.60±0.03) × 10-6 S cm-1. This polymer’s great thermal stability properties make it suitable for outdoor application where high temperature due to sun exposure is common. Furthermore, PUA prepared gel-like properties to make it a suitable candidate for preparing a gel polymer electrolyte.
... The epoxidized sunflower oil (ESO) was then washed with warm water to remove residual contaminants. Diethyl ether was used to enhance the water separation [15] . The washed organic layer was also dried with centrifugation to remove water traces in the epoxidized oil. ...
... The other new peaks at 3373.35 cm -1 for ESO and at 3374.51 cm -1 for ESOME are attributed to the hydroxyl functional group, derived from the epoxy functional group via partial epoxy ring opening reaction. The epoxy ring opening reaction could occur either by acid catalysis in the presence of water Scheme 1. Reaction for the synthesis of ESOME from ESO. associated with aqueous solution of H 2 O 2 used [15] . The peak in the spectrum of ESOME at 1739.92 cm -1 indicates the shifting of C=O absorption band and the characteristic ester band at 1027.80 cm -1 , these results indicate that the functional group has been converted into -COOC-for the three ester functions [23,24] . ...
The use of mixtures of nontoxic and biodegradable plasticizers coming from natural resources is a good way to replace conventional phthalates plasticizers. In this study, two secondary plasticizers of epoxidized sunflower oil (ESO) and epoxidized sunflower oil methyl ester (ESOME) were synthesized and have been used with two commercially available biobased plasticizers; isosorbide diesters (ISB) and acetyl tributyl citrate (ATBC) in order to produce flexible PVC. Different mixtures of these plasticizers have been introduced in PVC formulations. Thermal, mechanical and morphological properties have been studied by using discoloration, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), tensile - strain and scanning electron microscopy (SEM). Studies have shown that PVC plasticization and stabilization were improved by addition of plasticizers blends containing ISB, ATBC, ESO and ESOME. An increase in the content of ESO or ESOME improved thermal and mechanical properties, whereas ESOME/ATBC formulations exhibited the best properties.
... Other examples of high content unsaturated fatty acid oils that can also be used for industrial production are mahu seed oil, jojoba oil, karanja oil, soybean oil, sunflower oil etc (Meyer et al., 2008). This study was aimed at characterizing extracted J. curcas and T. peruviana oils from their oil bearing seeds as a way of optimizing their utility. ...
... curcas oil as a result of the presence of HCN (Meyer et al., 2008). ...
Thevetia peruviana and Jatropha curcas oils were cold extracted from their seeds using petroleum ether as extracting solvent. Characterization of the extracted vegetable oils showed that oil yield was greater than 50 % from both seeds. The moisture content of the extracted vegetable oils was less than 0.1 %, while their specific gravities were 0.908 and 0.907 for T. peruviana and J. curcas oil respectively. The refractive index and viscosity of the oils are 1.440 and 152.9 mPa.s for T. peruviana oil, 1.465 and 156.8 mPa.s for J. curcas oil respectively. The chemical properties of the oils showed free fatty acid values of the T. peruviana and J. curcas oil to be within the range of other vegetable oils. The iodine values of the oils confirmed the liquid nature of the oils. The results obtained revealed that the extracted vegetable oils are of good quality for cosmetics, soap, paint, and polyurethane productions, because of their high yield among other properties. The vegetable oils are not good for cooking, because of their inedible nature (free fatty acid is greater than 4 mgKOH/g in J. curcas oil and T. peruviana oil contains toxic cardiac glycoside).
... Because of high reactivity of oxirane ring, epoxides can also act as raw materials for alcoholysis, acidolysis and polymer [9][10][11]. Epoxidation of vegetable oil such as rapeseed, soybean, jatropha, karanja, mahua, cotton seed and canola oil were investigated [12][13][14][15][16][17]. ...
... Oxirane ring cleavage could perform by acid-catalyzed ring opening in the presence of water. During the epoxidation reaction, the presence of water in the aqueous phase owing to the reduction of hydrogen peroxide to water by in situ epoxidation [13]. Hence, an optimal formic acid mole ratio has to achieve to get a high %RCO product and minimize the oxirane ring cleavage. ...
The aim of this study is to optimise the epoxidation of linoleic acid of Jatropha curcas oil. This experiment was carried out with performic acid generated in situ by using hydrogen peroxide and formic acid. The method was evaluated on different parameters such as reaction temperature, mole ratios of formic acid to ethylenic unsaturation and hydrogen peroxide to ethylenic unsaturation. The optimum relative conversion into oxirane (80.4%) and conversion of iodine (94.7%) was achieved with ~70% yield at the condition of 45°C reaction temperature, formic acid to ethylenic unsaturation mole ratio of 2.0, hydrogen peroxide to ethylenic unsaturation mole ratio of 12.0 for 2 hours of reaction time. The epoxidized linoleic acid was characterized by using Fourier transform infrared (FTIR) spectroscopy and NMR analysis. The result was also found that the formations of an epoxide and oxirane ring cleavage were both occurred at the same time if low amount of hydrogen peroxide was used. © 2015, Malaysian Society of Analytical Sciences. All rights reserved.
... There are several works on producing epoxidized Jatropha oil (Daniel et al., 2011;Goud et al., 2007;Meyer et al., 2008). For example Daniel et al. (2011) applied Sharpless epoxidation of Jatropha oil by using dichloromethane, pyridine and methyltrioxorhenium catalyst with 30% hydrogen peroxide. ...
... It was observed that the inactive hydroxyl group was not consumed upon introduction of diisocyanate and no urethane group was observed. Factors such as solvent-free epoxidation and relatively high temperature induced erroneous side products as appeared on the FTIR spectrum of epoxidized Jatropha oil which was also reported others (Cai et al., 2008;Meyer et al., 2008). Reaction temperature of epoxidation imposes great impact toward formation of epoxy group quantitatively despite the fact that excess hydrogen peroxide was used. ...
... Therefore, in both the cases, the optimum concentration of H 2 O 2 required to get maximum conversion was 3 mol. The utilization of excess of H 2 O 2 for the epoxidation of karanja oil and its derivatives was in accordance with the studies of Meyer et al. 29 on conventional epoxidation of soybean oil and jatropha oil. The degree of conversion of these oils into their epoxidized oils highly depended on the excess utilization of H 2 O 2 in order to obtain high epoxy content in the respective oils. ...
... An excess amount of hydrogen peroxide was needed in the reaction in order to achieve maximum epoxidation. 29 Therefore, the mole ratio of HCOOH: H 2 O 2 was increased to 2:8 and maximum epoxidation was achieved. ...
Lubricant base stocks of epoxidized oil and its alkyl esters namely epoxidized karanja fatty acid methyl, butyl, 2-methyl-1-propyl, and 2-ethylhexyl esters were synthesized from renewable nonedible source karanja oil (Pongamia glabra). The reaction was carried out using peroxy formic acid (HCOOH) generated in situ, 30 wt % aqueous hydrogen peroxide (H2O2) by monitoring oxirane oxygen value. The optimized conditions to obtain epoxidized products were oil/ester: HCOOH: H2O2 (1:2:8/1:1.5:3 mol/mol/mol). The epoxidized products were obtained in 90–97% conversion by GC analysis. All the products were characterized by GC, GC-MS, IR, 1H NMR spectral studies. The synthesized products were evaluated for physicochemical and lubricant properties. Based on viscosity index all the products belong to group III, category of base fluids as per API classification. Expecting pour point values that are on higher side, other lubrication properties such as viscosity, VI, flash point, Cu corrosion value, and air release value were found to be good.
... The epoxidation of plant oil using peracids is one of the most important steps and a useful modification process toward the double bonds because the epoxides are reactive intermediates that can be converted to other functional groups through ring-opening reactions [18]. Plant oils with high content of unsaturated fatty acid are used to produce high epoxy functionality materials [19]. Epoxidized plant oils products from the epoxidation process can be used as high-temperature lubricants [20], plasticizers [21] and high temperature coating materials [22]. ...
Palm oil has become one of the potential renewable resources in biolubricant application. However, the direct application of palm oil as a biolubricant is restricted due to its low oxidative stability and poor low temperature properties. These drawbacks can be overcome by molecule structural redesign through chemical modification process. Palm oil (PO) was modified via epoxidation, ring opening and esterification process. The epoxidized palm oil (EPO) was prepared by using an in-situ performic acid catalyst. Then, EPO was ring-opened using oleic acid in the presence of p-toluenesulfonic acid (PTSA) as a catalyst and further esterification with oleic acid using sulfuric acid as catalyst. The molecular structure confirmation of modified palm oils was proven through the oxirane oxygen content (OOC) value, iodin value, hydroxyl value, Fourier transformation infra-red (FTIR), proton and carbon nuclear magnetic resonance (1 H-NMR and 13 C-NMR) spectroscopy analysis. Results showed that the conversion of PO into EPO has improved its oxidative stability (190 °C). While, the esterification process has resulted in branching and bending in the molecule structure of the final product (palm oil dioleate, PODO), which improved its pour point (-10 °C), flash point (315 °C) and viscosity index (146). These make PODO suitable to be used in biolubricant application. Abstrak Minyak sawit merupakan salah satu sumber yang boleh diperbaharui yang berpotensi dalam penghasilan biopelincir. Walaubagaimanapun, penggunaan secara terus minyak sawit sebagai biopelincir adalah terhad disebabkan oleh kestabilan oksidatif yang rendah dan sifat suhu rendah yang lemah. Kelemahan ini boleh diatasi dengan ubahsuai struktur molekul melalui proses pengubahsuaian kimia. Minyak sawit (PO) diubahsuai melalui proses pengepoksidaan, pembukaan gelang dan pengesteran. Minyak sawit terepoksida (EPO) dihasilkan menggunakan mangkin asid performik yang dijana secara in-situ. Seterusnya, EPO ditindakbalaskan melalui pembukaan gelang menggunakan asid oleik dengan kehadiran p-toluena asid sulfonik (PTSA) sebagai mangkin dan diikuti dengan pengesteran dengan asid oleik dengan menggunakan mangkin asid sulfurik. Pengecaman struktur molekul minyak sawit terubahsuai dibuktikan melalui nilai kandungan oksigen oksiran, nilai iodin, nilai
... The un- saturation present (double bond) in vegetable oils can be chemically modified to form epoxidized vegetable oils [17][18][19]. Epoxidation of double bond has been studied in many papers [20][21][22][23][24]. Epoxidation is generally performed using organic peracids formed in situ via the attack of H 2 O 2 on a carboxylic acid in aqueous solution [22]. ...
... A variety of chemical modifications of vegetable oil are possible through the reactive carbon to carbon double bond functionality. Among possible chemical modification reactions of the vegetable oil is epoxidation reaction which is a commercially important reaction in organic synthesis since the high reactivity of oxirane rings makes them to be readily transformed into desired product (Meyer et al., 2008). The technologies use to produce epoxides from the vegetable oil are: (i) epoxidation with molecular oxygen (Guenter et al., 2003) (ii) epoxidation with halohydrin (Guenter et al., 2003); (iii) epoxidation with organic and inorganic peroxide (Sharpless et al., 1983); and (iv) epoxidation with percarboxylic acid (Warwel and Klass 1995). ...
... Previously, the methods reported to carry out epoxidation reaction uses different reagents and catalysts such as (a) percarboxylic acids [15], (b) organic and inorganic peroxides [16], (c) halohydrines with hypohalous acids [15], and (d) molecular oxygen with silver as catalyst [17]. In most of the cases, it was observed that the reaction time for getting higher levels of conversion (in the range of 80-90%) to the epoxide usually varied from 6 to 20 h [18][19][20]. On the industrialized level, the epoxidation reaction is currently carried out using peracid, which is prepared in-situ via carboxylic acid and hydrogen peroxide, in the presence of acid catalysts like sulfuric or phosphoric acid. ...
The present work reports the use of ultrasonic irradiation for enhancing lipase catalyzed epoxidation of soybean oil. Higher degree of unsaturated fatty acids, present in the soybean oil was converted to epoxidized soybean oil by using an immobilized lipase, Candida antarctica (Novozym 435). The effects of various parameters on the relative percentage conversion of the double bond to oxirane oxygen were investigated and the optimum conditions were established. The parameters studied were temperature, hydrogen peroxide to ethylenic unsaturation mole ratio, stirring speed, solvent ratio, catalyst loading, ultrasound frequency, ultrasound input power and duty cycle. The main objective of this work was to intensify chemoenzymatic epoxidation of the soybean oil by using ultrasound, to reduce the time required for epoxidation. Epoxidation of the soybean oil was achieved under mild reaction conditions by indirect ultrasonic irradiations (using ultrasonic bath). The relative percentage conversion to oxirane oxygen of 91.22% was achieved within 5 h. The lipase was remarkably stable under optimized reaction conditions, later was recovered and reused six times to produce epoxidized soybean oil (ESO).
... JO is known as an oleic-linoleic oil. (Meyer et al., 2008) One of the important properties in the characterisation of epoxy vegetable oil is the determination of the oxirane-oxygen content (OOC), in order to ensure the epoxy groups are present in the products. Epoxy resins with a high OOC are desired in the production of polymer. ...
The non-edible seed oil of the Jatropha plant is a renewable and sustainable material to produce vegetable oil-based epoxy and epoxy acrylate as raw polymeric material. The objective of this study is to synthesis Jatropha seed oil-based epoxy and acrylate epoxy resins through conventional methods. An epoxy ring of Epoxidised Jatropha Oil (EJO) was formed through an in-situ epoxidation process using hydrogen peroxide and formic acid as an oxygen donor and oxygen carrier respectively. Acrylated Epoxidised Jatropha Oil (AEJO) was produced by reacting EJO with acrylic acid with the existence of triethylamine and 4-methoxyphenol as a catalyst and inhibitor respectively. The measured oxirane-oxygen content (OOC) of EJO was 4.99%. The acid value of the AEJO was determined at 4.42 mg KOH/g. Both the EJO and AEJO were characterised by FTIR and 1H NMR spectroscopies.
... JO is known as an oleic-linoleic oil. (Meyer et al., 2008) One of the important properties in the characterisation of epoxy vegetable oil is the determination of the oxirane-oxygen content (OOC), in order to ensure the epoxy groups are present in the products. Epoxy resins with a high OOC are desired in the production of polymer. ...
Sixteen (16) crossbred (White Fulani, Muturu & Keteku) calves aged 7-10 months and with an average weight of 69.78 ± 8.81 kg were sampled in a 12-week experiment to evaluate the response of calves to supplementation of legume - based concentrate diets. These calves graze on natural pastures. The sampled calves were allotted in a completely randomised design into four treatment groups and offered 25% Leucaena leucocephala, Enterolobium cyclocarpum and Glricidia sepium based concentrate diets and natural pastures (control) for treatments 1 - 4 respectively. Data were collected on feed intake, weight gain, nutrient digestibility, nitrogen balance, blood profile and faecal egg count of calves. The supplementation of forage legume concentrate diets improved (P < 0.05) DM intake and weight gain of calves with best results were observed in calves fed Glricidia sepium concentrate diets with 450.56 g/day and 188.45 g/day respectively. Nutrient digestibility (%) and nitrogen balance varied (P < 0.05) across treatment groups. Blood parameters did not differ (P > 0.05) across treatments and falls within the normal range for healthy calves, while the supplementation of forage legume concentrate diets reduced (P < 0.05) faecal egg count (egg/g) to ascertain the level of worm burden in calves. The study concluded that supplementation with legume concentrate diets improved the performance of calves with Gliricidia forage supplemented concentrate diet recommended for calves' optimum performance.
... The unsaturation present (double bond) in vegetable oils can be chemically modified to form epoxidized vegetable oils [17][18][19]. Epoxidation of double bond has been studied in many papers [20][21][22][23][24]. Epoxidation is generally performed using organic peracids formed in situ via the attack of H 2 O 2 on a carboxylic acid in aqueous solution [22]. ...
In this work, a novel vegetable oil-based polymers were prepared by epoxidation of soybean oil (SBO) and castor oil (CO) followed by ring opening reaction of epoxidized oil with polyether amine and poly propylene glycol. The prepared polymers were characterized by FTIR and GPC. The properties of vegetable oils and epoxidized vegetable oil (EVO) were studied. The prepared polymers were employed as novel polymeric dispersants for pigment dispersion in solvent based printing ink application. The mechanical and optical properties of prepared ink were studied. The net technical properties of the new ink formulations are relatively comparable to the prepared printing ink from standard polymeric dispersant. The polymeric dispersant 2 (PD2) and polymeric dispersant 4 (PD4) gave the best optical and mechanical properties among the prepared polymers.
... It was then dried overnight with magnesium sulphate. The ethyl acetate solvent used in the mixture to extract oil was removed using a rotary evaporator [6]. ...
Neopenthyl glycol dioleate (NPGDO) is a biolubricant base that was formed via esterification process with oleic acid. The presence of oleic acid leads to poor oxidative stability. In this study, epoxidation reaction between NPGDO, formic acid and hydrogen peroxide has been carried out to produce epoxidized NPG dioleate (ENPGDO) which acts as the intermediate of biolubricant. Epoxidized oil can be further modified for better properties. The temperature for this reaction was 40 °C and the molar ratio of NPGDO:formic acid:hydrogen peroxide was 1:3:4. The reaction had taken place for 3 hours. The presence of the epoxy in the product was confirmed through Fourier Transform Infrared (FTIR). The structure of ENPGDO was confirmed using both proton and carbon Nuclear Magnetic Resonance (¹H-NMR and 13C-NMR) analysis. The product was found to have 218 (viscosity indeks), 205 °C (flash point), -18 °C (pour point) and 197 °C (oxidative stability). The relative conversion of oxirane (RCO) for ENPGDO was 97.5%. © 2016, Malaysian Society of Analytical Sciences. All rights reserved.
... A variety of epoxidized oil has been produced. These epoxidized oils were used as intermediate products to manufacture diversifying end products that were useful for industrial uses (Dinda et al. 2008;Goud et al. 2006;Jia et al. 2011;Meyer et al. 2008;Milchert & Smagowicz 2008). The oxirane ring on epoxidized oils could react with alcohol compounds through alcoholysis and generates a compound with the hydroxyl and ether group, as can be seen in Figure 1. ...
Hydroxy-ether-PO0 was synthesised via alcoholysis reaction of epoxidized palm olein (EPO0). The experimental design was conducted using response surface methodology (RSM) based on 3 factors; reaction time, reaction temperature and catalyst loading. Responses such as percentage of conversion and percentage of yield were determined using statistical software 'Design Expert 9'. Hydroxy-ether-PO0 showed the presence of proton peak attached to the carbon of ether (3.2, 3.5 ppm) and proton of the hydroxyl (4.8 ppm). The presence of carbon peak bonded to hydroxyl was detected at chemical shift 75 ppm and carbonyl carbon of ether at 72 ppm.
... Pelbagai jenis minyak terepoksida telah dihasilkan. Minyak-minyak terepoksida tersebut telah digunakan sebagai produk pertengahan dalam menghasilkan pelbagai produk akhir yang berguna kepada industri (Dinda et al. 2008;Goud et al. 2006;Jia et al. 2011;Meyer et al. 2008;Milchert & Smagowicz 2008). Gelang oksirana pada sebatian terepoksida boleh bertindak balas dengan sebatian beralkohol secara alkoholisis untuk menghasilkan sebatian yang mempunyai kumpulan hidroksil dan eter seperti Rajah 1. Proses pembukaan gelang bermangkin asid menggunakan sebatian beralkohol ini bergantung kepada jenis alkohol yang digunakan (Wade 2006 Malaysia adalah antara negara pengeluar utama minyak sawit mentah (CPO) di dunia dan ini dapat memberikan kelebihan kepada Malaysia untuk memajukan industri pengeluaran produk berasaskan minyak sawit olein (PO o ). ...
Hydroxy-ether-POo (80% of yield) was synthesised through oxirane cleavage of epoxidized palm olein (EPOo) using alcoholysis process. An optimum oxirane cleavage has been obtained with 99.2% yield using sulphuric acid 3% v/wt at 80°C for 30 min. The proton-nuclear magnetic resonance (1H-NMR) spectrum of hydroxy-ether-POo showed the presence of proton peak attached to the carbon of ether (3.2, 3.5 ppm) and proton of hydroxy (4.8 ppm). The carbon-nuclear magnetic resonance (13C-NMR) spectrum of hydroxyl-ether-POo showed the presence of carbon peak bonded to hydroxyl (75 ppm) and carbonyl carbon on ether (72 ppm). While, kinematic viscosity of Hydroxy-ether-POo was 234.4 cSt (40°C) and 28.1 cSt (100°C) with the viscosity index of 156. © 2016, Penerbit Universiti Kebangsaan Malaysia. All rights reserved.
... Bio-renewable materials, such as plant oils and unsaturated fatty acid derivatives, have recently received increasing attention as a means of addressing environmental and economic concerns. Epoxidized oils are currently produced by the epoxidation of plant oils such as soybean, linseed oil [1] and Jatropha curcas seed oil [2]. ...
Monoepoxidation linoleic acid (MEOA) has advantages for industrial applications. MEOA was synthesized using immobilized Candida antarctica lipase (Novozym 435®). At optimum conditions, higher yield (82.14 %) and medium oxirane oxygen content, OOC (4.91 %) of MEOA were predicted at 15 µL of H2O2, 120 mg of Novozym 435® and 7 hours of reaction time. Fourier Transform Infrared Spectroscopy (FTIR) spectra of the MEOA showed monoepoxide group at 820 cm-1. 1H NMR analysis confirmed the monoepoxide group at 2.92 – 3.12 ppm while the monoepoxide signals of 13C NMR appear at 54.59 – 57.29 ppm. LC-MS analysis shows that of MEOA gives m/z at 296.22 as final product. MEOA exhibited good pour point (PP) of -41 ºC. Flash point (FP) of MEOA increased to 128 ºC comparing with 115 ºC of linoleic acid (LA). In a similar fashion, viscosity index (VI) for LA was 224 generally several hundred centistokes (cSt) more viscous than MEOA 130.8. MEOA was screened to measure their oxidative stability (OT) which was observed at 168 ºC. It is evident that increasing the hydrogen peroxide amount has a strong effect on the reaction kinetics; however, a large excess of hydrogen peroxide results in accumulation of peracid in the final product. © 2016, Malaysian Society of Analytical Sciences. All rights reserved.
... Lee et al. (2009) reported that FTIR was not only practised to confirm the formation of epoxy product, but also to monitor the potential side reactions, i.e. ring opening. The main signals present in FTIR functional groups of WCOME and its epoxide are reported in Table 4. Meyer et al. (2008) described that via oxirane ring opening reaction, OH-functional groups can be derived from epoxy functional groups. In this study, WCOME epoxide spectra exhibited with no trace of OH absorption peak approximately at 3000e3500 cm À1 , which indicates that no oxirane cleavage was observed during epoxidation. ...
This communication bridges the gap between conventional and alternative (renewable) lubricant basestocks in the lubricant industry. Waste cooking oil methyl esters (WCOME) originated from soybean oil was prepared by aiming at the maximum esters conversion. Esters conversion were confirmed and supported by thin layer chromatography and nuclear magnetic resonance spectral techniques (1H, 13C). WCOME bio-lubricant basestock was synthesized via In-situ epoxidation using acidic ion-exchange resin as a heterogeneous catalyst. A statistical experimental design, response surface methodology (RSM) was implemented to optimize the experimental conditions and to understand the interactions among the process variables. The optimum conditions inferred from the RSM were: temperature, 53.71 °C; catalyst loading, 28.17 wt%; time, 7.51 h; and H2O2, 1.72 mol. Products was confirmed and characterized by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FTIR) and oxirane analysis by HBr titration method. At this optimum condition maximum epoxide content was found to be 5.8 mass%. Physico-chemical properties of WCOME and its epoxide were determined by standard methods and compared. Characterization results revealed that the structurally modified WCOME epoxide had improved viscosity and thermo-oxidative stability compared with unmodified WCOME. Overall, outcomes of the physico-chemical characterization data indicated that prepared epoxide can act as an alternative lubricant basestock for various industrial applications.
... The level curves do not effectively represent the values observed experimentally, however, the performance of the biolubricant was higher compared with the other results found in its planning matrix, concluding that the percentages of selected additives provide superior performance to the base oil.Table 4 presents the results of the characterizations obtained for the biolubricants of passion fruit oil in natura (PFO) and with additives (PFOA), epoxidized passion fruit oil (EPFO) and with additives (EPFOA), moringa oil in natura (MO) and with additives (MOA), and epoxidized moringa oil (EMO) and with additives (EMOA), as well as the characterizations of commercial lubricants VG100 and R150.Table 4, one can observe that the iodine value decreases after the epoxidation of in natura oils, while the amount of oxygen as oxirane increases. These results confirm that the process of epoxidation for both in natura oils occurred (Adhvaryu & Erhan, 2002; Petrovic et al., 2002; Dinda et al., 2008; Meyer et al., 2008; Milchert et al., 2010; Mushtaq et al., 2013). It is observed that the presence of the additive increases the viscosity of the in natura passion fruit oil without additives (PFO) and the in natura moringa oil without additives (MO), and that after the epoxidations, this increase also occurs. ...
The aim of this work is to develop new biolubricants based on epoxidized vegetable oils, optimizing formulations with an additive package by experimental design. A 2³ factorial design with center points was used to determine optimal conditions for anti-wear, corrosion inhibition, extreme pressure, and antioxidants to be applied with formulations with epoxidized passion fruit and moringa oils. The lubricants obtained were characterized in accordance with DIN 51524 (Part 2 HLP) and DIN 51517 (Part 3 CLP) standards. The epoxidation process improved the oxidative stability and the acid value of both pure vegetable oils. Furthermore, the presence of epoxidized oils improved the solubilisation of the additives, increasing the fluids' performances. Regarding their suitability as lubricants, epoxidized moringa oil with additives presented the best results, followed by epoxidized passion fruit oil with additives, epoxidized moringa oil, epoxidized passion fruit oil, pure moringa oil and, finally, pure passion fruit oil.
... Preparation of the hydroxylated fatty acid (HFA) involved sequential oxidization and hydrolysis steps [10][11][12]. The synthetic route of HFA was represented in Figure 1. ...
The aim of this work was to synthesize a high-temperature polyol ester from Jatropha oil. The synthesis process was accomplished via chemical modifications involving epoxidation to remove the double bonds in Jatropha oil, hydrolysis to add hydroxyl groups, and then esterification with pentaerythritol to form the saturated polyol ester. The high decomposition temperature 359°C of the polyol ester was determined by thermogravimetric analysis. The lower peroxide value 0.07 meq/kg and iodine value 0.02 mg I2/100 g of the polyol esters were also determined.
... Vegetable sources such as soy bean and jatropha oil have high content of unsaturated fatty acid. These acids are used in the reaction to produce high epoxy functionality materials [4]. In addition, plant seeds are sustainable and their oils are less harmful to the human health, and are suggested as potential rubber process oil in the rubber compounding. ...
Epoxidized oil (EO) is a sustainable oil that can be obtained form edible or non-edible naturals oil. The incorporation of epoxidized oil can increase the green component in rubber compound. It can contributes to worldwide technology specially in green tyre manufacturing. Epoxidized oil has the potential to replace aromatic oil (AO) to rubber and polymer industry. The effect of incorporation of EO and AO into natural rubber vulcanizates (NR) was studied via tensile and tear strength tests according to ISO 31-1977 and ISO 6133, respectively. Tensile strength of AO value showed greather value compared to EO. Gradual increases of elongation were observed form both AO and EO. Both moduli at 100% and 300% elongation, showed reductions as oil loading were increased. The tear strength results showed that tearing energy insignificantly increased with oil loading. EO compound was found to possess higher tearing energy compared to AO compound for most composition except for 15 pphr EO.
... J. curcas seed oil and soybean oil have high a content of unsaturated fatty acids that can be converted to epoxy fatty acids, as reported by [16]. The plant oil-based epoxies are sustainable, renewable, and biodegradable materials that can replace petrochemical-based epoxy materials in some applications. ...
Vegetable oils have different unique properties owing to their unique chemical structure. Vegetable oils have a greater ability to lubricate and have higher viscosity indices. Therefore, they are being more closely examined as base oil for biolubricants and functional fluids. In spite of their many advantages, vegetable oils suffer from two major drawbacks of inadequate oxidative stability and poor low-temperature properties, which hinder their utilization as biolubricant base oils. Transforming alkene groups in fatty acids to other stable functional groups could improve the oxidative stability, whereas reducing structural uniformity of the oil by attaching alkyl side chains could improve the low-temperature performance. In that light, the epoxidation of unsaturated fatty acids is very interesting as it can provide diverse side chains arising from the mono- or di-epoxidation of the unsaturated fatty acid. Oxirane ring opening by an acid-catalyzed reaction with a suitable reagent provides interesting polyfunctional compounds.
... There are several methods that can be used to prepare EVO [3][4][5][6][7][8], the most common of which uses the oxidation by peroxy acids (peracids) formed by reaction of formic or acetic acid with hydrogen peroxide (Fig. 1). On the laboratory scale, it can also be more convenient to make use of commercially available m-chloroperbenzoic acid (MCPBA), a more stable peroxy acid [5]. ...
Non-aqueous reversed phase liquid chromatography/electrospray mass spectrometry (NARP-LC/ESI–MS) was used to monitor the epoxidation of canola oil by performic acid. The reaction was sampled at regular intervals over 28 h and analyzed by NARP-LC/ESI–MS in order to observe the formation of partially epoxidized reaction intermediates and the fully epoxidized products. The experiment focused on the transformation of triacylglycerols (TAG) with 54 carbons in the fatty acyl chains and between 2 and 7 double bonds which account for >93 % of the oil. NARP-LC/ESI–MS allowed determination of the time required for full epoxidation of the oil. It was shown that complete epoxidation of TAG with low numbers of double bonds occurs more rapidly than for those with many double bonds. Furthermore, it was observed that epoxidation of multiply unsaturated TAG occurs via a sequential process in which partially epoxidized intermediates are consumed to form other more highly epoxidized compounds as the reaction proceeds. Data obtained by flow-injection ESI–MS was found to be comparable to that obtained from NARP-LC/ESI–MS for monitoring intermediates and products and could be adapted for in-process reaction monitoring.
Currently, there was an increasing demand for biobased materials because of the depletion of petroleum‐based resources and the growing awareness toward environmental protection. For that reason, researchers find interest in the utilization of plant oils for the preparation of bioresins and their biobased blends, mainly in the polymer industry for future applications. Plant oil‐based bioresins are a better alternative for petroleum‐based epoxy resins owing to their economical, renewable, nontoxic, and environment‐friendly nature. On the other hand, thermoset epoxy resins exhibit excellent properties and are widely employed for various applications such as painting, coatings, adhesives, aerospace, and electric industry. However, because of their signifying insufficient impact strength, toughness, and poor crack resistance, they finally result in brittleness after curing, limiting their applications in certain areas. Recently, plant oils have been utilized effectively for blending in epoxy polymers and thereby reducing the dependency on petroleum‐based materials. Therefore, the toughness of the materials without altering their mechanical and thermal properties is enhanced. The present chapter covers the utilization of bioresins synthesized from plant oils and their biobased blends with DGEBA epoxy resin.
Introduction. Application of renewable raw materials for manufacturing non-toxic components of polymer materials is of great practical interest. Cyclic carbonates on the base of epoxidated rubber tree oil could be seen as a promising alternative of fossil fuels. The ability of compounds containing cyclic carbonates to interact with primary amines and to form urethane and hydroxyl groups makes them rather efficient modifiers of amine-toughened epoxy compounds on the base of low-molecular diane oligomers. Introduction of cyclic carbonates enhances impact behavior of epoxy materials as well as their adhesion and strength properties. Materials and methods. Epoxy resin ED-20 was used for the research, as a cross-linking agent for cold toughening aminealkylphenol AF-2 was used; cyclic carbonates of epoxidated soy oils and rubber tree oil were applied as modifiers. Adhesional strength of bond joints has been determined in compliance with the GOST 28840-90, abrasive hardness of epoxy compound samples has been tested by the vertical optical caliper IZV-1. Results. When applying two-stage technology for obtaining epoxy cyclic carbonate compounds, there has been appeared a significant increase of adhesion to aluminum. This effect could be even more noticeable with increasing temperature during the stage of mixture of the amine toughener with the cyclic carbonate modifier. High viscosity of cyclic carbonate modifiers complicates the process of mixing components of the epoxy compound and correspondingly its application as a backing of glues and linings. The authors researched cyclic carbonates of epoxidated soy oil with various averaged functionality as modifiers. Application of epoxy materials CESO-75 as a modifier has proven to be more forward-thinking for the reasons of cost-efficiency and for operating and technological properties. CESO lowers the coefficient of static friction for epoxy materials together with enhancing their abrasion hardness. Conclusions. Cyclic carbonates of epoxidated plant oils (soy oil and rubber tree oil) as rather efficient non-toxic modifiers of epoxy polymers are of practical interest. They are produced on the base of annually renewable plant raw materials. Their application enables to enhance abrasion hardness and adhesion properties of epoxy compounds and also improve their antifriction properties.
The vegetable oils are one of the most perspective renewable raw materials due to biodegradability and non-toxicity inherent them and also wide area of application. The vegetable oils-these are fats and lipids containing triglyceride molecules. Due to increase of ecological problems (complexity of waste utilization, non-degradable biological resources, greenhouse effect, etc.) and the expected reduction of the oil reserves, the renewable biological resources of plant origin are of particular importance. The epoxidated vegetable oils are one of the largest industrial applications of the vegetable oils and are widely used as the plasticizers and intermediate products for synthesis of polyols or unsaturated polyesters. The high-efficient monomers, polymers and composites on the basis of the epoxidated vegetable oils can successfully substitute the analogous products prepared from epoxide resin on the basis of the oil. In generalized review the methods of preparation, properties and areas of applications of the epoxidated vegetable oils published in scientific literature are considered
Renewable resourced polymer composites from vegetable oils and bio-fibers are receiving increasing attention from various industries due to their characteristics of being less heavy, environment friendly, and biodegradable. Lignocellulosic natural fibers have immense potential to be used as reinforcing fillers due to their characteristics of being less expensive, abundant obtainability, lower density, higher specific strength and modulus, and good interfacial strength with thermoset polymers. In this chapter, epoxidized nonedible linseed and castor oils are proposed as a diluent to petro-based epoxy in formulating toughened bio-based copolymers. Unidirectional sisal fibers were reinforced within a network of such bio-epoxy copolymers in order to achieve an optimal stiffness–toughness balance. Cardanol based phenalkamine, a bio-renewable crosslinker, is used to develop well toughened sustainable and green composite materials. The composites were subjected to various thermal, mechanical, dynamic mechanical, and morphological tests to investigate the impact of nonedible epoxidized oils and sisal fibers in addition to the petro-based epoxy matrix. The present study shows the method for design and development of novel sustainable green composites with higher bio-source content (>65%) meant for shock absorbing applications. These green materials may find good space in making high-performance engineering applications in automotive, structural, construction, and building sectors.
The goal of this thesis was to design thermally responsive polyol resins that would be compatible with isocyanates. Two approaches were made to reach this goal, the first involved functionalizing soybean oil and the second involved post-polymerization modification of a methacrylate based resin.
A soybean based coating with thermally responsive Diels-Alder linkages has been prepared following an automotive two-component formulation. The resulting coatings displayed the capability to be healed following physical deformation by a thermal stimulus, and such a material has significant potential for end users. Various curing agents were employed, and resulted in variation of scratch resistance and re-healablity. Different thermally responsive soybean resins were synthesized to have varying amounts of reversible and nonreversible linkages when incorporated into the coating.
Additionally, different isocyanates were added at differing ratios of NCO:OH in search of the optimum coating. It was found through the analysis of re-healabilty, hardness, gloss, and adhesion that the optimal combination was an acetylated resin (no irreversible crosslinks) with 54% reversible Diels Alder linkages at an NCO:OH ratio of 5:1 using isophorone diiscocyanate. Materials were evaluated via differential scanning calorimetry (DSC), scratch resistance, Koenig hardness, gloss measurements, and topographical analysis.
In the second project, copolymerization of methyl methacrylate and 2-isocyanatoethyl methacrylate via free radical polymerization was done to synthesize a polymer with pendant isocyanates. The isocyanate was used as a chemical handle to incorporate Diels-Alder linkages into the PMMA resin. The PMMA resin with Diels-Alder linkages was successfully synthesized and incorporated into a polyurethane gel as proven via 1H NMR and IR. The gel showed thermal reversibility at 120°C due to retro-DA reaction via DSC as well as thermally reversible bulk properties.
The rising demand for environmentally acceptable lubricant has led researchers to look to vegetable oils as an alternative to petroleum based lubricants. Vegetable oils have radically distinctive properties owing to their unique chemical structure which have greater ability to lubricate and have higher biodegradability. In spite of advantages, they are limited to inadequate thermo-oxidative stability and poor low-temperature properties which hinder their utilization. In the present study in order to produce a bio lubricant with good thermo-oxidative stability, rapeseed oil was subjected to two different chemical modification techniques viz., epoxidation method and successive transesterification method. The thermo-oxidative stability of formulated oil was analysed using Thermo Gravimetric Analysis (TGA). TGA analysis divulges that the thermo-oxidative stability of rapeseed oil was greatly improved with the epoxidation method in comparison with the successive transesterification method.
Two different novel high-functional bio-based resins from Methoxylated Sucrose Soyate Polyol (MSSP) and methacrylated epoxidized sucrose soyate (MAESS) were used as matrices for composites. Vinyl ester reinforced with flax fiber and E-glass fiber were also produced as the references to highlight the performance of bio-based composites. An appropriate processing conditions for MSSP and MAESS resins using compression molding was established to fabricate high fiber volume content composites. Mechanical properties of composites were assessed by tensile, flexural, interlaminar shear strength (ILSS), nano-indentation, and impact strength. Scanning Electron Microscopy (SEM) of fractured surfaces of flexural specimens were examined to investigate the fiber-matrix interface behavior. MSSP and MAESS resins reinforced with E-glass fiber performed similarly if not superior to previous bio-based and petroleum-based composites studied Tensile strength and modulus of E-glass reinforced MSSP were higher up to 40% and 75% respectively, compared to existing studies. For flexural strength and modulus 130% and 110% improvements were observed. The tensile strength and modules of MAESS and vinyl ester resins reinforced with E-glass fibers are 532 MPa, 36.79 GPa and 536 MPa, 36.40 GPa, respectively. The impact strength of the composites with MAESS resin reinforced with E-glass fibers was 237 kJ/m2, whereas that of the vinyl ester resin reinforced with same E-glass fiber was 191 kJ/m2. Results of SEM images along with flexural strength, interlaminar shear strength and impact tests revealed better wetting of fibers by matrix, stronger adhesion between fiber and matrix and greater interfacial bonding compared to corresponding E-glass/vinyl ester composites. The composites made from flax fiber with MSSP or MAESS resins achieve similar properties to E-glass/MSSP and E-glass/MAESS in terms of specific mechanical properties. Moreover, flax/MSSP and flax/MAESS composites perform similarly, if not superior to previous
bio-based and petroleum based composites studied. A micromechanical model and an analytical approach were also developed to predict the stress relaxation response of the flax/MSSP composite material consisting linear viscoelastic flax fiber and bio-based PU matrix. A good agreement between the micromechanical modeling data and experimental results was observed for the linear viscoelastic response of the bio-based composite.
In this study acrylated epoxidized flaxseed oil was synthesized and then characterized by spectroscopic techniques. Triglycerides are the main constituents of flaxseed oil and the carbon-carbon double bond is the reaction site for epoxidation. Flaxseed oil was epoxidized by adding formic acid and hydrogen peroxide. Acrylic acid was then added to produce acrylated epoxidized flaxseed oil (AEFO). The change in the structure of the fatty acids chain after the epoxidation and acrylation reactions was measured and characterized by Hydrogen nuclear magnetic resonance spectroscopy (1H NMR) and Fourier transform infrared spectroscopy (FTIR). The FTIR spectra of epoxidized flaxseed oil and flaxseed oil shows the disappearance of the =C–H (3012 cm−1) and C=C (1654 cm−1) peaks. The FTIR spectra confirmed the formation of AEFO since the presence of hydroxyl group (–OH) was shown by the peak at 3455 cm−1 and the acrylate group (–CH=CH2), which was indicated by the peaks at 1406, 984 and 812 cm−1. The changes in peaks of the 1H NMR spectra also confirmed the formation of AEFO. The number of acrylate groups/molecule of triglyceride was found to be 2.6 from 1H NMR spectra.
The effect of ultrasonic reactors on the epoxidation of sunflower oil was investigated using two different sonochemical reactors such as ultrasonic horn and ultrasonic bath. The optimized parameters for the synthesis were established followed by scale up studies. Use of combination of ultrasonic bath and mechanical agitation gave maximum conversion to oxirane oxygen as 91.1%. The synthesized epoxidized sunflower oil (ESNO) was used as plasticizer in polyvinyl chloride sheets and the performance was evaluated by thermogravimetric analysis and mechanical testing methods. It has been established that ESNO plasticizer has ability to replace dioctyl phthalate (DOP) giving a sustainable and greener approach.
This study aimed to develop new hydraulic biolubricants based on vegetable oils epoxidized via performic acid, and to investigate their tribological behavior under conditions of boundary lubrication. The tribological performance of the developed lubricants was analyzed in an HFRR (high frequency reciprocating rig) apparatus. The coefficient of friction, obtained during the contact and the formation of the lubricating film, was measured. The characterizations were performed according to DIN 51524 norm (Part 2 HLP) and DIN 51517 norm (Part 3 CLP) standards. The wear was evaluated by optical and scanning electron microscopy (SEM). The results showed that adding extreme pressure (EP) and antiwear (AW) additives in fluids improves significantly the tribological properties. It was observed that the addition of EP and AW additives to in natura vegetable oils of passion fruit and moringa did not reduce the wear considerably. The biolubricants developed from passion fruit and moringa oils, modified via epoxidation, displayed satisfactory tribological properties being considered as potential lubricants, able to replace commercial mineral-based fluids.
Polymeric materials from renewable resources have attracted a lot of attention in recent years. The development and utilization of vegetable oils for polymeric materials are currently in the spotlight of the polymer and chemical industry, as they are the largest renewable platform due to their universal wide availability, ingrained biodegradability, low cost, and excellent environmental aspects (i.e., low ecotoxicity and low toxicity toward humans). These excellent natural characteristics are now being taken advantage of in research and development, with vegetable oil derived polymers/polymeric materials/composites being used in numerous applications including paints and coatings, adhesives, and nanocomposites. The aim of this review paper is to give a fundamental description of the various vegetable oil applications in polymer materials and its recent developments. Particular emphasis will be placed on study and main application of triglyceride based additive for polymer and to give the reader an insight into the main developments is discussed.
In the present communication waste cooking oil (WCO) epoxide was synthesized by in-situ epoxidation technique using hydrogen peroxide (H2O2) as oxygen donor in presence of acidic ion exchange resin (IER) as catalyst. The main objective of this study was
to establish an optimum reaction condition for maximum oxirane oxygen content (i.e., OOC) and to study the effects of process variables and their interaction to maximise OOC (response). Response surface methodology (RSM) was employed for statistical analysis and to optimize the reaction variables
in the epoxidation of WCO. Central composite rotatable design (CCRD) was adopted to study the effect of time (h), H2O2 molar ratio (mol), catalyst loading (wt%) and temperature (°C) on response. The outcomes of RSM analysis indicate that most of the linear, quadratic
and cross variables were showing highly significant (P < 0.0001) effect on response. A second-order model satisfactorily fitted the data (R
2 = 0.9935). Based on the quadratic analysis optimum condition for this reaction was found to be H2O2
1.68 mol (H2O2) to ethylenic unsaturation molar ratio), catalyst loading 16.75 wt%, temperature 54 °C and reaction time 11.45 h, at this condition % OOC was found to be 6.2%. The product was confirmed by 1H NMR and FTIR spectral analysis. After structural
modification physico-chemical properties of epoxidised WCO were found to be improved compared to WCO. This indicates that WCO epoxide could act as a potential alternative for the conventional lubricant base-stock.
In this study, jatropha oil was reacted with glycerol and toluene diisocyanate to obtain urethane oil at hydroxyl to isocyanate ratio of 1:0.8 with methanol acting as a blocking agent. The prepared urethane oil was characterized for molecular weight and its properties were determined and compared with those of the linseed oil-modified and commercial urethane oils. It was found that the jatropha-modified urethane oil was a yellowish viscous liquid with a number-average molecular weight of 2,673. The urethane oil prepared from jatropha oil took longer time to dry than the linseed oil-modified and commercial urethane oils. Results showed that the film properties of the jatropha-modified urethane oil were comparable to those of the commercial urethane oil. The film exhibited good hardness, excellent flexibility and adhesion, and high impact strength. Additionally, it also showed excellent water resistance but only fair alkali resistance.
Camelina oil is a promising material for the biopolymer industry due to its high unsaturated fatty acid content of 90%. The aim of this study was to optimize the epoxidation parameters of camelina oil. The epoxidation reaction of camelina oil was completed with formic acid and hydrogen peroxide. Catalyst ratio, reaction time, and temperature effects on the epoxidation reaction were studied. The optimum epoxy content of 7.52 wt% with a conversion rate of 76.34% was obtained for camelina oil using excess hydrogen peroxide and a molar ratio of formic acid of less than 1 for 5 h at 50 °C. We also found that epoxidation efficiency is significantly affected by fatty acids composition, structure, and distribution. The di-hydroxylized epoxidized camelina oil showed higher peel adhesion when it was formulated with epoxidized soybean oils. Epoxidized camelina oil has potential industrial applications in the field of pressure sensitive adhesives, coatings, and resins.
Recently, aromatic oil (AO) is one of the substances that is typically used as a processing aid especially for high filler loadings in formulating rubber compound. Aromatic oil has disadvantages in that, it is hazardous to environment, toxic and has been labeled as carcinogenic. In this research, an epoxidised oil (EO) and aromatic oil were used to investigate the effect incorporation of oil onto the SBR/NR natural rubber vulcanizates (NR). From the result obtained, EO showed shorter cure time and scorch time as the oil loading were increased up to 20 pphr of EO. Physical properties such as hardness and rebound resilience of NR/EO vulcanisate were also investigated upon exposure to different humidity level in humidity chamber. At room temperature, the hardness of EO loading onto the SBR/NR vulcanisate is lower than AO loadings. Hardness was slightly decreased with increasing rate of humidity. There is great difference in hardness and rebound resilience values between AO and EO. Both hardness and rebound resilience were not affected by humidity. This implies the existence of good filler interaction with EO and rubber which do not impart changes in the hardness and resilience properties of rubber compound. Epoxidised oil has great promising potential to replace the carcinogenic aromatic oil as it has good overall performance and renewable in nature .
Green resins based from sustainable resources are a requirement nowadays to replace non environmental coatings. Low (VOC) content epoxy which competes with conventional well established coating and high price could be derived from oil. UV curable resin is typically low VOC systems and offer advantages of rapid ambient cross linking and more energy efficient. Epoxy resins must have fast curing and low shrinkage upon cure which will give advantages to devices performance but epoxy resins are expensive and hence renewable resources from vegetable or non food oil can be used as raw materials.
We investigate new polyols based on castor oil for polyurethane. In order to introduce primary alcohol groups, which exhibit higher reactivity with isocyanate than secondary alcohol groups, the secondary alcohol groups on castor oil were modified with maleic anhydride and aminoalcohol derivatives (-R-OH). The reactions with various molar ratio of castor oil and maleic anhydride were done at relatively low reaction temperature in the absence of catalyst. The polyols based on castor oil with flexible side-chains exhibit better miscibility with conventional synthetic polyols.
With environmental and toxicity concerns becoming more critical, there are increasing efforts to remove phthalates from polymer compounds around the globe more rapidly. Phthalates can be replaced by natural products; in particular, those obtained from vegetable oils and fats. In the present study, a natural-based plasticizer, synthesized by epoxidation of non-toxic rice bran oil (RBO) with peroxy acid generated in situ has been added to poly(vinyl chloride). The influence of various reaction parameters on epoxidation was studied by investigating the reaction ratio, temperature, reaction time and stirring speed. Epoxidized rice bran oil (ERBO) obtained from an optimized reaction condition was analyzed by iodine number and oxirane content. FTIR was used to analyze epoxy group formation. Product ERBO was obtained with 82 % oxirane conversion within 3 h of reaction period. PVC sheets were formulated using a conventional plasticizer di-(octyl) phthalate and was partially replaced by synthesized ERBO. The effect of ERBO addition was tested by mechanical properties (tensile strength, modulus, elongation-at-break, shore D hardness) and compared with commercially available ESBO (epoxidized soybean oil). ERBO presented fairly good incorporation and plasticizing performance, as demonstrated by the results of mechanical properties, exudation, migration tests, thermal stability by thermogravimetric analysis, T
g values as shown by differential scanning calorimetry, replacing about 60 % of the total plasticizer.
Vegetable oils are being investigated as potential source of environmentally favorable lubricants over synthetic products. Jatropha curcas L. oil (JO) identified as a potential raw material for biodiesel was explored for its use as a feedstock for biolubricants. Epoxidized jatropha oil (EJO) was prepared by peroxyformic acid generated in situ by reacting formic acid and hydrogen peroxide in the presence of sulfuric acid as catalyst. Almost complete conversion of unsaturated bonds in the oil into oxirane was achieved with oxirane value 5.0 and iodine value of oil reduced from 92 to 2 mg I2/g. EJO exhibited superior oxidative stability compared to JO. This study employed three antioxidants such as butylated hydroxy toluene (BHT), zinc dimethyl dithiocarbamate (ZDDC), and diphenyl amine (DPA) and found that DPA antioxidant performed better than ZDDC and BHT over EJO compared to JO. The lubricating properties of EJO and epoxy soybean oil (ESBO) are comparable. Hence, EJO can be projected as a potential lubricant basestock for high temperature applications.
Novel epoxidized hemp oil-based biocomposites containing jute fibre reinforcement were produced at the Centre of Excellence in Engineered Fibre Composites (CEEFC) owing to the need to develop new types of biobased materials. Mechanical properties (tensile, flexural, Charpy impact and interlaminar shear), thermo-mechanical properties (glass transition temperature, storage modulus and crosslink density) and moisture-absorption properties (saturation moisture level and diffusion coefficient) were investigated and compared with samples containing commercially produced epoxidized soybean oil and a synthetic bisphenol A diglycidyl ether-based epoxy control, R246TX cured with a blend of triethylenetetramine and isophorone diamine. Scanning electron microscopy was also performed to investigate the fibre– matrix interface. Epoxidized hemp oil-based samples were found to have marginally superior mechanical, dynamic mechanical and similar water-absorption properties in comparison to samples made with epoxidized soybean oil bioresin; however, both sample types were limited to bioresin concentrations below 30%. Synthetic epoxy-based samples exhibited the highest mechanical, dynamic mechanical and lowest water-absorption properties of all investigated samples. This study has also determined that epoxidized hemp oil-based bioresins when applied to jute fibre-reinforced biocomposites can compete with commercially produced epoxidized soybean oil in biocomposite applications.
Epoxy acrylate has been widely used as optical resin for applications
such as cladding, the core of a waveguide, and other photonic devices.
In this study, sustainable resin from edible oil was used as an
alternative to epoxy acrylate. Structural features and the transmission
of planar thin-film resin from an ultraviolet-visible spectroscopy
(UV-VIS) spectrometer were investigated upon UV exposure. It was found
that high transmission still persists for all samples with and without
an UV absorber for exposed and unexposed samples. The film was found to
absorb strongly below 400 nm. A change in the cut-off wavelength was
observed upon exposure. Thin-film hardness and its dynamic indentation
in the load-unload mode with different test forces were evaluated.
Vickers hardness and the elastic modulus were determined for unacrylated
epoxidized soybean oil (ESO) and acrylated epoxidized soybean oil
(AESO). It was found that the AESO has a higher Vickers hardness and
elastic modulus than those of unacrylated thin film. The Vickers
hardness and elastic modulus were found to increase as the applied test
force increased. The refractive index, thickness, and modes present were
characterized from a spin-coated planar thin film. The refractive index
in the transverse electric mode (TE) and transverse magnetic mode (TM)
were determined and compared for unacrylated and acrylated epoxidized
oil.
In this study aliphatic polyacids were synthesized using palm acid oil (PAO) and sunflower oil (SFO) via addition reaction technique. The synthesized materials were characterized using Fourier-transform infra-red (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-ToF-MS) and thermo-gravimetric analysis (TGA). Mixing formic acid and hydrogen peroxide with PAO or SFO at the ratio 3:10:1 produced the lowest iodine value of 10.57 and 9.24 respectively, indicating the increase in epoxidization of both oils. Adding adipic acid to the epoxidized oils at a ratio of 1:10 increases the acid values of SFO and PAO to 11.22 and 6.73 respectively. The existence of multi-acid groups present in synthesized polyacid was confirmed by MALD-ToF-MS. This feature indicates a possible value to the biomaterials development.
The epoxidation reaction of vegetable oils has been looked upon as an alternative option for synthesis of epoxides with an objective of replacing the petroleum-based epoxides. The present work illustrates epoxidation of soybean oil using tetra-n-butyl ammonium bromide as a phase transfer catalyst (PTC) in the presence of sonochemical devices such as ultrasonic horn and ultrasonic bath. Effect of various parameters such as pulse of ultrasound, power of ultrasound, effect of external temperature, amount of phase transfer catalyst, type of reactor configuration on the extent of conversion, etc. have been investigated. Under optimised conditions, the iodine value of oil was reduced from 132 to almost 19 at temperature of 80 °C using the ultrasonic horn. The intensification of epoxidation of soybean oil using ultrasound was observed in terms of substantial reduction in the reaction time for similar levels of conversion. It was found that the relative percentage conversion to oxirane using the conventional method was about 87% in 10 h while using ultrasound horn, almost 83% conversion was obtained in 4 h. The present work has clearly illustrated the utility of sonochemical reactors for intensification of epoxidation reaction opening a new opportunity for commercial exploitation.
Eight lipases were studied in hydrolysis reactions toward the goal of selectively removing saturated fatty acids from epoxidized soybean oil. Commercially available epoxidized soybean oil has about 18% saturated fatty acids, which manifest themselves as branches when used in polymers. The removal of these fatty acids creates a potentially valuable degree of freedom in the processing of soybean oil for polymer applications.Hydrolysis was achieved with seven of the eight enzymes with the epoxy functionality increasing reaction rates and changing selectivities. Lipases from Penicillium roquefortii, Mucor javanicus, Rhizomucor miehei and Pseudomonas sp. showed selectivity toward diepoxy acyl moieties. Aspergillus niger lipase selectively hydrolyzed saturated fatty acids in soybean oil but the lipase was not selective with epoxidized soybean oil. Penicillium camembertii lipase was found to be an inactive enzyme for triglyceride substrates. The selectivity of Candida rugosa toward saturated fatty acids increased in epoxidized soybean oil. Burkholderia cepacia lipase had selectivity toward both palmitic acid and stearic acid but not the epoxy acyl moieties. A hypothesis is proposed that explains unexpected trends in the selectivities of the lipases.
Vegetable oils and fats are important constituents of human and animal foodstuffs. Certain grades are industrially used and, together with carbohydrates and proteins, are important renewable resources compared to fossil and mineral raw materials, whose occurrence is finite. In concepts for new products, the price, performance, and product safety criteria are equally important and have a correspondingly high importance right at the start of product development. To ensure a high degree of product safety for consumers and the environment, renewable resources have often been shown to have advantages when compared with petrochemical raw materials and can therefore be regarded as being the ideal raw material basis. Results from oleochemistry show that the use of vegetable fats and oils allows the development of competitive, powerful products, which are both consumer-friendly and environment-friendly. Recently developed products, which fit this requirement profile, are the anionic surfactants cocomonoglyceride sulfate and the nonionic sugar surfactant alkyl polyglycoside. These products are used especially as mild surfactants in cosmetic formulations. In polymer applications derivatives of oils and fats, such as epoxides, polyols, and dimerizations products based on unsaturated fatty acids, are used as plastic additives or components for composites or polymers like polyamides and polyurethanes. In the lubricant sector fatty acid- based esters have proven to be powerful alternatives to conventional mineral oil products.
Multiple novel vegetable oil-based polyols were synthesized from the reaction-addition to epoxidized soybean oil (ESBO) by a series of acid acyl moieties derived from vegetable oils. The acid acyl moieties were linoleic acid (LA), ricinoleic acid (RC), ricinoleic acid estolide (RC estolide) and hydrolyzed bodied soybean oil (HBSBO). LA and RC were commercially available but RC estolide and HBSBO were synthesized by enzymatic catalytic reactions. In the reaction-addition, ESBO was heated with the acid acyl moieties at 170 °C, atmospheric pressure without any catalyst and solvent. The synthesized vegetable oil-based polyols had acid numbers less than 10 (mg KOH/g), hydroxy numbers of 82–152 (mg KOH/g), and hydroxyl equivalent weights of 370–680. The polyols made from RC estolide and HBSBO had improved numbers of OH equivalent weight comparing to the numbers from alkoxyl hydroxyl soybean oil which is widely used commercial soy-based polyols.
A series of esters of palm stearin and palm olein were synthesized by alcoholysis using KOH as catalyst. Epoxidations were carried out in situ by the method of peroxyformic and peroxyacetic acids. The alcohols employed ranged from methanol to dodecyl alcohol. The esters were evaluated as plasticizers for poly(vinyl chloride) (PVC). Esters of palm stearin had poorer compatibility and might be used only as secondary plasticizers. Promising results, however, were obtained for epoxy esters of palm olein which were found to be good plasticizers for PVC. Long chain epoxy esters were less compatible while their short chain counterparts were too volatile for thermal stability. Epoxy butyl esters of palm olein were found to be most promising. The solubility parameters δ for a series of oleates, palmitates and epoxy esters were calculated using Small's method with Fredors' molar volume. Epoxystearates have higher δ values than the corresponding oleates and palmitates, in agreement with the experimental findings that epoxidation improves compatibility. Molar volumes calculated by Fredors' method were found to be in remarkable agreement with the experimental values for oleates and palmitates but were overestimated for epoxystearates. It was concluded that the palmitates were largely responsible for the poorer compatibility for the epoxy esters of palm olein prepared from higher alcohols.
Alkyl nitrate derivatives of soybean oil, castor oil, olive oil, and canola oil were synthesized and evaluated as cetane improvers for use in diesel fuel. Of several nitration methods evaluated, mixtures of nitric acid with acetic anhydride provided quality product while allowing nitration at ambient temperatures. Nitration using neat concentrated nitric acid was also effective in certain applications. Significant process development strides were made in the areas of reducing nitration costs, reducing risks associated with this nitration chemistry, and identifying processes that simultaneously address constraints on processing viscosities, product solubility, and waste minimization. Some of the products were effective cetane improvers, but their performance was not as consistent as that of the commercial product 2-ethylhexylnitrate.
Fifty vegetable oil-based polyols were characterized in terms of their hydroxyl number and their potential of replacing up to 50% of the petroleum-based polyol in waterborne rigid polyurethane foam applications was evaluated. Polyurethane foams were prepared by reacting isocyanates with polyols containing 50% of vegetable oil-based polyols and 50% of petroleum-based polyol and their thermal conductivity, density, and compressive strength were determined. The vegetable oil-based polyols included epoxidized soybean oil reacted with acetol, commercial soybean oil polyols (soyoils), polyols derived from epoxidized soybean oil and diglycerides, etc. Most of the foams made with polyols containing 50% of vegetable oil-based polyols were inferior to foams made from 100% petroleum-based polyol. However, foams made with polyols containing 50% hydroxy soybean oil, epoxidized soybean oil reacted with acetol, and oxidized epoxidized diglyceride of soybean oil not only had superior thermal conductivity, but also better density and compressive strength properties than had foams made from 100% petroleum polyol. Although the epoxidized soybean oil did not have any hydroxyl functional group to react with isocyanate, when used in 50 : 50 blend with the petroleum-based polyol the resulting polyurethane foams had density versus compressive properties similar to polyurethane foams made from 100% petroleum-based polyol. The density and compressive strength of foams were affected by the hydroxyl number of polyols, but the thermal conductivity of foams was not. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007
Vegetable oils are biodegradable and therefore good candidates for environmentally friendly base stocks. They have excellent lubricity, but poor oxidation and low temperature stabilities. For this study, synthetic lubricant basestocks with oxidative stabilities and pour points comparable with commercial synthetic lubricant basestocks have been prepared by reacting epoxidized soybean oil with Guerbet alcohols. Four different Guerbet alcohols, C12-, C14-, C16-, and C18-Guerbet alcohols were used. Reaction of epoxidized soybean oil with a Guerbet alcohol in the presence of a catalytic amount of sulfuric acid provided open-ringed products. 1H NMR has shown that transesterification follows after ring-opening reaction under the given reaction conditions. Two types of ring-opened products, 0%- and 100%-transesterified products, could be obtained under controlled reaction conditions. Pour points of the ring-opened products ranged from −18 to −36 °C without pour point depressant (PPD) and from −21 to −42 °C with 1% of PPD. Acetylation of hydroxy groups in the ring-opened products further lowered pour points that ranged from −27 to −42 °C without PPD and from −30 to −48 °C with 1% of PPD. Oxidative stability was examined using a modified Penn State microoxidation test and compared with those of synthetic lubricant basestocks and mineral oil. Oxidative evaporations of two selected products in the microoxidation test were similar to mineral oil and less than synthetic lubricant-based oils, polyalphaolefin (PAO4) and diisododecyl adipate. Deposits of these products were similar to synthetic lubricant-based oils and less than mineral oil.