Morphology and photoelectrochemical properties of TiO2 electrodes prepared using functionalized plant oil binders

Chemically functionalized plant oils, viz. acrylated epoxidized soybean oil (AESO) and maleinized acrylated epoxidized soybean oil (MAESO), were used as bio-based binders for the TiO₂ electrodes of dye-sensitized solar cells (DSSC). The surface roughness and number of appropriate pores were increased in the TiO₂ films prepared using the plant oil binders in comparison with the film prepared using polyethylene glycol (PEG), due to the larger number of functionalities. The short circuit photocurrent (I_SC) and open circuit photovoltage (V_OC) were increased, and the conversion efficiency was significantly improved, in the cell using the plant oil binders.     

Polymerization of epoxidized triglycerides with fluorosulfonic acid

The use of triglycerides as agri-based renewable raw materials for the development of new products is highly desirable in view of uncertain future petroleum prices. A new method of polymerizing epoxidized soybean oil has been devised with the use of fluorosulfonic acid. Depending on the reaction conditions, one can get a viscous oil or a solid as the reaction product. The reaction mechanism has been studied through a systematic examination of the fluorosulfonic acid-initiated reaction of epoxidized methyl oleate and epoxidized methyl linoleate. Through ¹³C NMR spectroscopy, the major species derived from fluorosulfonic acid-initiated polymerization of epoxidized soybean oil have been determined. The effects of temperature, initiator dosage, and reaction time have been studied and shown to affect the nature of polymer products obtained and the distribution of different chemical species present.     

Analysis of thermal,oxidative and cold flow properties of methyl and ethyl esters prepared from soybean and mustard oils

Oilseed crop with high oil content and promising ecological adaptability are potential sources for competitive biodiesel production. This study investigates the scope of utilizing biodiesel development through the methyl and ethyl ester from soybean and mustard oil as an alternative fuel. Methyl and ethyl esters of oils having different fatty acids compositions such as soybean (SOME and SOEE) and mustard oil (MUME and MUEE) were prepared by transesterification with methanol and ethanol in the presence of an alkali-KOH catalyst. The gas chromatographic (GC) analysis of oil samples revealed that primary fatty acid composition in soybean oil was linoleic acid (C_18:2, 51.93%), followed by oleic acid (C_18:1, 22.82%), palmitic acid (C_16:0, 11.56%), linolenic acid (C_18:3, 5.95%) and stearic acid (C_18:0, 4.32%). Whereas, the main components in mustard oil were erucic acid (C_22:1, 32.81%), oleic acid (C_18:1, 24.98%), eicosenoic acid (C_20:1, 10.44%), linolenic acid (C_18:3, 8.61%) and palmitic acid (C_16:0, 2.80%). The physicochemical properties (acid value, iodine value, calorific value, flash point, pour point etc.) of methyl and ethyl ester samples were estimated and found to be within the acceptable range of ASTM D6751 standards specifications. The prepared esters and oil samples were examined for cold flow properties by differential scanning calorimetry (DSC). Results revealed better cold flow properties for MUME (−2.55 °C) and MUEE (−3.10 °C) than SOME (3.21 °C) and SOEE (1.83 °C) due to more unsaturated fatty acid content in MU. Thermal and oxidative stability of samples was determined by thermogravimetric analysis (TG) and differential thermal analysis (DTA). The thermal and oxidative stability ranking of the samples was in the order of oil > methyl esters > ethyl esters.

     

Reactive Extraction of Citric Acid Using Tri-n-octylamine in Nontoxic Natural Diluents: Part 1—Equilibrium Studies from Aqueous Solutions

Use of cheap, nontoxic, and selective solvents could economically provide a solution to the recovery of carboxylic acids produced by the bioroute. In this regard in the present paper, reactive extraction of citric acid was studied. Problems encompassing the recovery of the acid ([H₃A] _aq ^o ?=?0.1?C0.8) was solved by using tertiary amine (tri-n-octylamine, TOA) in natural diluents (rice bran oil, sunflower oil, soybean oil, and sesame oil). TOA was very effective in removal of acid providing distribution coefficient (D) as high as 18.51 (E%?=?95?%), 12.82 (E%?=?93?%), 15.09 (E%?=?94?%), and 16.28 (E%?=?94?%) when used with rice bran oil, sunflower oil, soybean oil, and sesame oil, respectively. Overall extraction constants and association numbers for TOA + rice bran oil, TOA + sunflower oil, TOA + soybean oil, and TOA + sesame oil were evaluated to be 35.48 (mol/l)^?1.46, 29.79 (mol/l)^?1.30, 33.79 (mol/l)^?1.51, and 37.64 (mol/l)^?1.65 and 1.46, 1.30, 1.51, and 1.65, respectively. Specific equilibrium complexation constants (K _E(n/m)) were also predicted using mathematical modeling.     

Non-conventional oils for biodiesel production: a study of thermal and oxidative stability

Vegetable oils with variable proportions of oleic, linoleic, and linolenic acids are more susceptible to oxidative processes. In this subject, this study evaluates the physical chemical properties and oxidative stability of non-conventional oils such as andiroba, babassu, sesame, oiticica, jatropha, and grape through accelerated oxidation techniques (pressurized differential scanning calorimetry, Rancimat and PetroOxy). It was verified that babassu and andiroba oil do not showed detectable induction period presenting high oxidative stability; moreover, it was observed that the enthalpic events occurred in 1.19, >10, 0.53, 0.49, 0.49, and 0.60 h for the andiroba oil, babassu oil, sesame seeds, jatropha, oiticica oils, and grapes, respectively, stimulating the conclusion of greater stability for the babassu oil.     

4-Vinylbenzenesulfonic acid adduct of epoxidized soybean oil: Synthesis, free radical and ADMET polymerizations

In this work new radically polymerizable triglyceride based monomers were synthesized by the reaction of epoxidized methyl oleate (EMO) and epoxidized soybean oil (ESO) with 4-vinyl benzene sulfonic acid (4VBSA). The products are 1-(4-vinylbenzene sulfonyl)oxy-2-alkonols of epoxidized soybean oil (SESO) and 1-(4-vinylbenzene sulfonyl)oxy-2-alkonols of epoxidized methyl oleate (SEMO). These adducts were characterized by ¹H NMR, ¹³C NMR, IR and CHNS elemental analysis. SESO was found to contain, on the average, 2.47 4VBSA units per triglyceride. SESO was free radically polymerized and co-polymerized with styrene and the mechanical and thermal properties of the resulting thermosets were determined by DMA, DSC and TGA. SEMO was used as a model compound to determine the efficiency of metathesis catalysts for these fatty acid derivatives. The second generation Hoveyda–Grubbs catalyst was found to give best yields. ADMET polymerization of SESO with this catalyst with and without solvent gave ∼80% yield of a thermoset polymer. Polymers obtained by free radical route swelled in water at room temperature, and hydrolyzed in water at 60 °C.     

Synthesis and Thermal Properties of Epoxidized Vegetable Oil

Summary: The novel potential epoxy resins, epoxidized soybean oil (ESO) and epoxidized castor oil (ECO), were synthesized and characterized. The cationic polymerization of ESO and ECO with a latent thermal catalyst, N‐benzylpyrazinium hexafluoroantimonate (BPH), was initiated at 80 and 50 °C, respectively. The cured ECO samples showed a higher T_g and lower coefficient of thermal expansion than those of ESO, due to the higher intermolecular interaction in the ECO/BPH system.

Relationships between ESO or ECO conversion and temperature in the polymerization with 1 wt.‐% BPH for 2 h.     

Bio-based removable pressure-sensitive adhesives derived from carboxyl-terminated polyricinoleate and epoxidized soybean oil

A novel kind of fully bio-based PSAs we re obtained through the curing reaction between two components derived from the plant oils:carboxyl-terminated polyricinoleate(PRA) fro m the castor oil and epoxidized soybean oil(ESO).The get content,glass transition temperature(Tg),rheological behavior,tensile strength,creep resistance and 180° peel strength of the PSAs were feasibly tailored by adjusting the component ratio of ESO to PRA.At low cross-linking level,the PSAs behaved like a viscous liquid and did not possess enough cohesiveness to sustain the mechanical stress during peeling,The PSAs cross-linked at or near the optimal stoichiometric conditions displayed an adhesive(interfacial) failure between the substrate and the adhesive layer,which were associated with the lowest adhesion levels.The PSAs with the dosage amount of ESO ranging from 10.20 wt% were tacky and flexible,which exhibited 1800 peel strength ranging from 0.4～2.3 N/cm;and could be easily removed without any residues on the adherend.The process for the preparation of the fully bio-based PSAs was environmentally friendly without using any orga nic solve nt or other toxic chemical,herein showing the great potential as sustainable materials.     

Epoxidation reactions with urea–hydrogen peroxide catalyzed by methyltrioxorhenium(VII) on niobia

Soybean oils (oleic, linoleic, and linolenic acids and their methyl esters) are epoxidized readily with urea–hydrogen peroxide (UHP) when methyltrioxorhenium(VII) supported on niobia is used as the catalyst in chloroform. Simple alkenes are epoxidized by the same method. The epoxide and not a diol is produced.     

EFFECT OF UNSATURATION OF C18 FATTY ACIDS AT LIQUID PARAFFIN-WATER INTERFACES

Abstract

Unsaturated C ₁₈ fatty acids are the largest constituents of the vegetable oils that are used in the pharmaceutical and cosmetic industries. To investigate effects of various vegetable oils on the stability of multiple emulsions, configuration of oleic, linoleic and linolenic acids at the liquid paraffin-water interface was studied by measuring the interfacial tensions and calculating the interfacial excess and molecular cross-sectional areas of the acids at 0.1 to 10% w/ w concentrations as well as of the pure acids. Linolenic acid produced the lowest interfacial tension followed by oleic and linoleic acids. The results have been explained in terms of preferential interfacial adsorption and hydrophobic hydration. Linolenic acid has the highest interfacial excess value of 2.24 × 10^?10moles/ cm² followed by oleic acid, 1.49 × 10^?1 moles/ cm² and linoleic acid,1.33 x 1010^?10 moles/ cm² The findings suggest that hydrophobic hydration of the fatty acids depends strongly on the number of the double bonds present. The study contributes to explaining stability problems involved in the vegetable oil based multiple emulsion systems.     

Thermal and mechanical properties of epoxy resin toughened with epoxidized soybean oil

A series of new modified epoxy resin (EP) cured products were prepared from epoxidized soybean oil and commercial epoxy resin, with methyl nadic anhydride as curing agent and 1-methylimidazole as promoting agent. The thermal properties of the resins were characterized by DMA and TG; DSC was used to determine the curing process. Fourier transform infrared spectroscopy was utilized to investigate their molecular structures and scanning electron microscopy was used to observe the micro morphology of their impact fracture surfaces. Tensile and impact testing was employed to characterize the mechanical properties of the cured products. The combination of commercial EP with 20 wt% ESO resulted in a bioresin with the optimum set of properties: 130.5 °C T _g, 396.9 °C T _50 %, 74.89 MPa tensile strength, and 48.86 kJ m^?2 impact resistance.     

New soybean oil–styrene–divinylbenzene thermosetting copolymers. II. Dynamic mechanical properties

A variety of new polymeric materials ranging from soft rubbers to hard, tough, and brittle plastics were prepared from the cationic copolymerization of regular soybean oil, low saturation soybean oil (LoSatSoy oil), or conjugated LoSatSoy oil with styrene and divinylbenzene initiated by boron trifluoride diethyl etherate (BF₃ · OEt₂) or related modified initiators. The relationship between the dynamic mechanical properties of the various polymers obtained and the stoichiometry, the types of soybean oils and crosslinking agents, and the different modified initiators was investigated. The room‐temperature storage moduli ranged from 6 × 10⁶ to 2 × 10⁹ Pa, whereas the single glass‐transition temperatures (T_g) varied from approximately 0 to 105 °C. These properties were comparable to those of commercially available rubbery materials and conventional plastics. The crosslinking densities of the new polymers were largely dependent on the concentration of the crosslinking agent and the type of soybean oil employed and varied from 74 to 4 × 10⁴ mol/m³. The T_g increased and the intensity of the loss factor decreased irregularly with an increase in the logarithmic crosslinking densities of the polymers. Empirical equations were established to describe the effect of crosslinking on the loss factor in these new polymeric materials. The polymers based on conjugated LoSatSoy oil, styrene, and divinylbenzene possessed the highest room‐temperature moduli and T_g 's. These new soybean oil polymers appear promising as replacements for petroleum‐based polymeric materials. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2721–2738, 2000     

Tethering versus Non‐Coordination of Hydroxy and Methoxy Side Chains in Arene Half Sandwich Dichloro Ruthenium Complexes

We are reporting on the hydroxyalkyl appended arene ruthenium half sandwich complexes [{η⁶‐C₆H₅(CH₂)_nOH}RuCl₂] (n = 2, 3) and the methyl ether of the hydroxypropyl derivative. Most significantly, a structural comparison between the hydroxypropyl complex 1a and its methyl ether 2a reveals, that the latter adopts the conventional dichloro bridged dimeric structure while 1a is a monomer. Coordinative saturation of the ruthenium centre is achieved by intramolecular coordination of the appended hydroxy function, thus rendering the functionalized arene an eight electron donor chelate ligand. The structure is further stabilized by intermolecular OH···Cl hydrogen bridges between a terminal chloride ligand of one and the coordinated hydroxy group of a neighbour molecule, resulting in a sheet structure. These intermolecular interactions appear to be even stronger in the hydroxyethyl analogue. Several phosphine adducts have been prepared from the hydroxy or alkoxy functionalized [(η⁶‐arene)RuCl₂]_n precursors, including water soluble P(CH₂OH)₃ adducts. Electrochemical properties of the phosphine adducts and of the dichloro bridged aryl ether complex 2a are also discussed.     

New soybean oil‐Styrene‐Divinylbenzene thermosetting copolymers—IV. Good damping properties

New polymeric materials have been prepared by the cationic copolymerization of regular soybean oil, low saturation soybean oil, i.e. LoSatSoy oil, or conjugated LoSatSoy oil with styrene and divinylbenzene, norbornadiene or dicyclopentadiene initiated by boron trifluoride diethyl etherate (BF ₃·OEt ₂) or related modified initiators. The effects of the stoichiometry, the type of soybean oil and the alkene comonomer on the damping behavior of the resulting polymers have been investigated. The damping properties have been quantitatively evaluated by the loss tangent maximum (tan δ) _max, ­the temperature range ΔT for efficient damping (tan δ > 0.3), and the integrals of the linear tan δ v. temperature curves (tan δ area, TA). These bulk materials are composed primarily of soybean oil‐styrene‐divinylbenzene random copolymers with considerable variability in the backbone compositions. The good damping properties of the soybean oil polymers are presumably determined by the presence of fatty acid ester side groups directly attached to the polymer backbone and the segmental heterogeneities resulting from crosslinking. In general, crosslinking reduces the (tan δ) _max and the TA values, but broadens the region of efficient damping (ΔT). Soybean oil polymeric materials with appropriate compositions and crosslink densities are capable of efficiently damping over a temperature region in excess of 110 °C and provide noise and vibration attenuation over broad temperature and frequency ranges. Copyright © 2002 John Wiley & Sons, Ltd.     

Preparative and scaled‐up separation of high‐purity α‐linolenic acid from perilla seed oil by conventional and pH‐zone refining counter current chromatography

α‐Linolenic acid is an essential omega‐3 fatty acid needed for human health. However, the isolation of high‐purity α‐linolenic acid from plant resources is challenging. The preparative separation methods of α‐linolenic acid by both conventional and pH‐zone refining counter current chromatography were firstly established in this work. The successful separation of α‐linolenic acid by conventional counter current chromatography was achieved by the optimized solvent system n‐heptane/methanol/ water/acetic acid (10:9:1:0.04, v/v), producing 466 mg of 98.98% α‐linolenic acid from 900 mg free fatty acid sample prepared from perilla seed oil with linoleic acid and oleic acid as by‐products. The scaled‐up separation in 45× is efficient without loss of resolution and extension of separation time. The separation of α‐linolenic acid by pH‐zone refining counter current chromatography was also satisfactory by the solvent system n‐hexane/methanol/water (10:5:5, v/v) and the optimized concentration of trifluoroacetic acid 30 mM and NH₄OH 10 mM. The separation can be scaled up in 180× producing 9676.7 mg of 92.79% α‐linolenic acid from 18 000 mg free fatty acid sample. pH‐zone refining counter current chromatography exhibits a great advantage over conventional counter current chromatography with 20× sample loading capacity on the same column.     

Isoxazole‐Embedded Allylic Zinc Reagent for the Diastereoselective Preparation of Highly Functionalized Aldol‐Type Derivatives Bearing a Stereocontrolled Quaternary Center

Highly functionalized aldol‐type products bearing a β‐quaternary center and a stereoselectively controlled γ‐hydroxy function are readily prepared by the diastereoselective addition of an allylic zinc reagent embedded in an isoxazole ring to various aromatic and heteroaromatic aldehydes, in the presence of Lewis acids, such as MgCl₂ or LaCl₃?2 LiCl. After reductive cleavage of the N?O bond by using Fe, NH₄Cl, aldol‐type products bearing a stereocontrolled β‐quaternary center and a γ‐hydroxy group were observed. The benzylic reactivity of the isoxazolylmethylzinc reagent towards other electrophiles, such as acid chlorides, aryl and allylic halides, as well as aldehydes in the presence of BF₃?OEt₂ are also described.     

2‐Ethyl‐6‐methylpyridin‐3‐ol and its salt bis(2‐ethyl‐3‐hydroxy‐6‐methylpyridinium) succinate

The title compounds, C₈H₁₁NO, (I), and 2C₈H₁₂NO⁺·C₄H₄O₄²⁻, (II), both crystallize in the monoclinic space group P2₁/c. In the crystal structure of (I), intermolecular O—H...N hydrogen bonds combine the molecules into polymeric chains extending along the c axis. The chains are linked by C—H...π interactions between the methylene H atoms and the pyridine rings into polymeric layers parallel to the ac plane. In the crystal structure of (II), the succinate anion lies on an inversion centre. Its carboxylate groups interact with the 2‐ethyl‐3‐hydroxy‐6‐methylpyridinium cations via intermolecular N—H...O hydrogen bonds with the pyridine ring H atoms and O—H...O hydrogen bonds with the hydroxy H atoms to form polymeric chains, which extend along the [01] direction and comprise R₄⁴(18) hydrogen‐bonded ring motifs. These chains are linked to form a three‐dimensional network through nonclassical C—H...O hydrogen bonds between the pyridine ring H atoms and the hydroxy‐group O atoms of neighbouring cations. π–π interactions between the pyridine rings and C—H...π interactions between the methylene H atoms of the succinate anion and the pyridine rings are also present in this network.     

Monitoring of thermal behavior and decomposition products of soybean oil

The thermal degradation and corresponding decomposition products of fresh and heat-treated soybean oil were investigated by synchronous thermal analyzer combined with Fourier transform infrared spectrometry and quadrupole mass spectrometry (STA–FTIR–QMS). Two longtime heat-treated soybean oil samples were aforehand prepared by consistently heating the fresh soybean oil for 50 and 100 h, respectively. N₂ and simulative air (N₂/O₂ = 4:1, volume) were used as the thermal reaction gas atmosphere. The results showed that one stage of mass loss appeared in analysis of the all oil samples under N₂ atmosphere condition and longtime heat pre-treatment had no effect on the thermal behavior of the soybean oil under N₂ atmosphere condition. However, four stages occurred in analysis of both untreated and heat-treated oil samples under the simulative air atmosphere condition. Longtime heat pre-treatment influenced the thermal behavior of the soybean oil in certain extent, which was reflected in the different mass loss values of the four stages. According to the infrared absorption profiles and MS spectra of the released compounds in vapor phase, H₂O, CO, CO₂, hydrocarbons (such as CH₄), and hydroxyl, carbonyl, and carboxyl-contained compounds have been confirmed. Therefore, STA–FTIR–QMS can be suggested as a promising technique for investigating of thermal degradation and monitoring the decomposition products of the evolving substances in edible oils.     

Three hydrates of the bisphosphonate risedronate,consisting of one molecular and two ionic structures

Three different hydrates of risedronate were obtained by varying the pH of a solution containing the compound. At the pH values used, the N atom of the pyridine group is protonated and the compounds are zwitterionic. Crystals obtained directly from the synthesis resulted in risedronate monohydrate, or [1‐hydroxy‐1‐phosphono‐2‐(pyridinium‐3‐yl)­ethyl]phosphonate monohydrate, C₇H₁₁NO₇P₂·H₂O, (I), in which just one phosphonate group is negatively charged. Recrystallizations at pH values of 2 and 4 yielded risedronate dihydrate, or sodium [1‐hydroxy‐2‐(pyridinium‐3‐yl)­ethane‐1,2‐diyl]­bis­(phosphonate) dihydrate, Na⁺·C₇H₁₀NO₇P₂⁻·2H₂O, (II). Finally, recrystallizations at pH values of 7 and 8 produced risedronate 2.5‐­hydrate, or sodium [1‐hydroxy‐2‐(pyridinium‐3‐yl)­ethane‐1,2‐diyl]­bis­(phosphonate) 2.5‐hydrate, Na⁺·C₇H₁₀NO₇P₂⁻·­2.5H₂O, (III). At these four pH values, both phosphonate groups in (II) and (III) are negatively charged and coordinated to an Na⁺ ion. Crystals of (II), i.e. those grown at pH values of 2 and 4, have isomorphous polymeric ion aggregate structures with geminal phosphonate and alcohol groups coordinated to the same Na⁺ ion. On the other hand, crystals of (III), i.e. those grown at pH values of 7 and 8, have isomorphism polymeric ion aggregate structures with geminal phosphonate and alcohol groups coordinated to different Na⁺ ions.     

Production of Human Milk Fat Replacement Rich of 1,3-dioleoyl-2-palmitoilglycerol From Enzymatic Interesterification Tripalmitin,Ethyl Oleate And Mixture of VCO,Soybean Oil And Fish Oil

Human Milk is naturally the only source of food for infant in their early life. It contains 2-6% lipid which provides about 50% of the total energy needed by the infant. Human milk fat (HMF) mainly as TAG with the specific fatty acid composition, palmitic acid (C16:0) (20-25%), which is primary located at sn-2 of glycerol bonds (70%) and oleic acid (C18:1), located at sn-1,3 (35%). HMF also provide fatty acids such as linoleic acid, linolenic acid, EPA, DHA and lauric acid that are very important for infant. The purposes of this research are to synthesize of 1,3-dioleoyl-2-palmitoilglycerol (OPO) and to determine the best composition of OPO, VCO, soybean oil and fish oil for HMFS production for infant formula. Interesterification of tripalmitin and ethyl oleate using immobilized lipase from Rhizomucor miehei (Lipozym RM IM) were used to synthesize of OPO. Interesterification product of mixed VCO, soybean oil and fish oil that are source of lauric acid, linoleic acid, α-linolenic, EPA and DHA, were formulated in mass ratio (58:20:20:2) and (70:18:10:2) for obtaining HMFS which have fatty acids composition similar or close to HMF. Composition of fatty acids from product were analyzed by GCMS. From this research, were obtained HMFS containing palmitic acid as much as 28.89% where 84.49% of that are located at sn-2 while sn-1,3 position are dominated by oleic acid as much as 55.11% from the total 38.7% and 70:18:10:2 w/w is the best composition of interesterification product, VCO, soybean oil and fish oil to obtain HMFS similar to HMF.