Modification of epoxidized soybean oil for lubricant formulations with improved oxidative stability and low pour point

To produce soybean oil-based lubricants with good oxidative stability and low pour point, epoxidized soybean oil (SBO) was chemically modified. Epoxidized SBO was reacted with various alcohols in the presence of sulfuric acid as a catalyst to give a ring-opened intermediate product. In this step, the epoxy group was transformed to the functional group of-CH(OR¹)CH(OH)-(where the R¹=methyl, 1-butyl, 2-butyl, 1-hexyl, cyclohexyl, 2,2-dimethyl-1-propyl, or 1-decyl). The ¹H nuclear magnetic resonance spectra of the products indicated that transesterification was accompanied by the ringopening reaction except when the bulky 2,2-dimethyl-1-propanol was used. Acid anhydride was used to esterify the hydroxy groups in the ring-opened product. This resulted in a fluid that is a lubricant candidate with the functional group of −CH(OR¹)CH(OCOR²)−. Pour point studies of the resulting products showed that the pour points varied with the substituents, R¹ and R². Products with R¹=CH₃(CH₂)₅₋ and R²=CH₃(CH₂)₂₋, (CH₃)₂CH−, or CH₃(CH₂)₄-showed the lowest pour points (−39, −39, and −45°C, respectively) when 1% of pour point depressant was added. For the oxidative stability test, two products, in which R¹, R²=CH₃(CH₂)₅₋, (CH₃)₂CH− and R¹, R²=CH₃(CH₂)₅₋, CH₃(CH₂)₄₋, were chosen for a modified Penn State micro-oxidation test. In the oxidative stability test, the products gave 69–71% of oxidative evaporation and 10–17% of tetrahydrofuran-insoluble deposits in 3 h at 175°C. The amounts of deposits were much lower than those of soybean oil (96%) and epoxidized SBO (83%) and even less than those of most petroleum-based lubricant basestocks (3–93%).     

Preparation, characterization and mechanical properties of epoxidized soybean oil/clay nanocomposites

New epoxidized soybean oil (ESO)/clay nanocomposites have been prepared with triethylenetetramine (TETA) as a curing agent. The dispersion of the clay layers is investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). XRD and TEM data reveal the intercalated structure of ESO/clay nanocomposites has been developed. The thermogravimetric analysis exhibits that the ESO/clay nanocomposites are thermally stable at temperatures lower than 180 °C, with the maximum weight loss rate after 325 °C. The glass transition temperature, T_g, about 7.5 °C measured by differential scanning calorimetry (DSC) and T_g about 20 °C measured by dynamic mechanical study have been obtained. The difference in the T_g between DSC and dynamic measurements may be caused by different heating rate. The nanocomposites with 5-10 wt% clay content possess storage modulus ranging from 2.0×10⁶ to 2.70×10⁶ Pa at 30 °C. The Young's modulus (E) of these materials varies from 1.20 to 3.64 MPa with clay content ranging from 0 to 10 wt%. The ratio of epoxy (ESO) to hydrogen (amino group of TETA) greatly affects dynamic and tensile mechanical properties. At higher amount of TETA, the nanocomposites exhibit stronger tensile and dynamic properties.     

Green approach for the preparation of biodegradable lubricant base stock from epoxidized vegetable oil

A novel process for the production of biodegradable lubricant-based stocks from epoxidized vegetable oil with a lower pour point via cationic ion-exchange resins as catalysts was developed. This involves two steps, first, ring-opening reactions by alcoholysis followed by esterification of the resultant hydroxy group in the first step.

The ring-opening reaction of epoxidized soybean oil with different alcohols such as n-butanol, iso-amyl alcohol and 2-ethylhexanol was carried out in presence of Amberlyst 15 (Dry) as a catalyst; identity of products was confirmed by IR and NMR. Pour points of the products were observed in the range of −5 to −15 °C. The hydroxy group of ring-opening product of n-butanol was further reacted with acetic anhydride in presence of catalyst Amberlyst 15 (Dry), which was previously used to carry out ring-opening reaction by alcoholysis and identity of the resulting product was confirmed by IR. Pour point of the resulting product was observed to be −5 °C.     

Polyols from epoxidized soybean oil and alpha hydroxyl acids and their adhesion properties from UV polymerization

Two types of biobased polyols, ESOGA and ESOLA, were synthesized from epoxidized soybean oil (ESO) with glycolic acid (GA) and lactic acid (LA), respectively, using a solvent-free/catalyst-free method. An ESO epoxy conversion rate of over 93% was achieved for both polyols. ESOGA has a weight-/number-average molecular weight (M_w/M_n) of 27,700/3900 g/mol and average hydroxyl functionality (f_OH) of 12.9, and ESOLA has M_w/M_n of 8800/3000 g/mol and f_OH of 11.7. The structures of the polyols were further characterized with Fourier transform infrared spectroscopy and ¹H-nuclear magnetic resonance. Rheology and thermal properties were studied with a rheometer and a differential scanning calorimeter. The polyols were polymerized with ESO to adhesive polymers using UV light in the presence of cationic photoinitiator. The curing rate decreased as the amount of polyol increased for resins based on ESOGA and ESOLA (EGA and ELA). With the same amount of polyol, ELA resins cured faster than EGA resins. The peel strength and tack of EGA and ELA adhesives increased significantly as the ratio of polyol in the resin increased. ELA exhibited obviously higher peel strength and tack than EGA with the same amount of polyol. All resin tapes exhibited high static shear values (20,000+min). Overall, both ESOGA and ESOLA exhibited great potential as polyols for pressure-sensitive adhesive applications.     

The study of epoxidized rapeseed oil used as a potential biodegradable lubricant

The application of epoxidized rapeseed oil as a biodegradable lubricant is described. The epoxidation treatment has no adverse effect on the biodegradability of the base stock. Epoxidized rapeseed oil has superior oxidative stability compared to rapeseed oil based on the results of both oven tests and rotary oxygen bomb tests. Moreover, the oxidative stability can be dramatically promoted by the addition of a package of antioxidants. The epoxidized rapeseed oil has better friction-reducing and extreme pressure abilities according to tribological investigations. Formation of a tribopolymerization film is proposed as explanation of the tribological performance of epoxidized rapeseed oil.     

Biobased nanocomposites from clay modified blend of epoxidized soybean oil and cyanate ester resin

Novel bio-based nanocomposites were prepared by blending surface modified natural clay with epoxidized soybean oil (ESO) and cyanate ester resin (CE). A convenient method was employed to modify the attapulgite (ATT) clay by adsorbing the poly(ethylene glycol) diglycidyl ether (PEGDE) onto the clay surface, which was confirmed by the appearance of a new peak of infrared spectroscopy due to hydrogen bonding and chelation. Thermogravimetic analysis (TGA) showed that the amount of PEGDE adsorbed on ATT was influenced by PEGDE concentration in acetone solution. Scanning electron microscope (SEM) and transmission electron microscope (TEM) results showed that nanoscaled ATT dispersed well in the blend of epoxidized soybean oil (ESO) before and after curing. The thermal-physical and mechanical properties were evaluated by dynamic mechanical analysis (DMA), TGA and tensile mechanical test. The nanocomposites showed higher glass transition temperature and modulus, and the tensile strength of the nanocomposites was reinforced as compared to that of ESO/CE blends.     

紫外光固化环氧豆油丙烯酸酯的制备与表征

将环氧大豆油与丙烯酸反应制备出环氧豆油丙烯酸酯预聚物,讨论了反应温度、反应时间、催化剂、阻聚剂的种类与用量对合成反应的影响,并用红外光谱对产物的结构进行了表征。研究结果表明其最佳反应条件是:催化剂三苯基膦,反应温度110℃,反应时间8h。该预聚树脂可用紫外光固化,其固化膜硬度达3H,且具有较好的柔韧性和附着力。     

Ion chromatographic determination of phosphorus and tungsten in epoxidized soybean oil

Soybean oil has been epoxidized with hydrogen peroxide in the presence of catalytic amounts of trioctylmethyl-ammonium tetra(diperoxotungsto)phosphate. A fast ion-exchange chromatographic method with suppressed conductivity detection has been developed for determining residual contents of tungsten and phosphorus in the oil. Tungsten and phosphorus could be determined at concentrations of 66 and 11 ppm, respectively. At tungsten and phosphorus concentrations of 1000 and 50 ppm, measured repeatabilities were 1.3 and 1.5%, respectively.     

涂料用环氧大豆油的研究进展

介绍了环氧大豆油在阳离子光固化体系、环氧豆油丙烯酸酯涂料及其他涂料体系的研究状况,并对其应用前景进行了展望。     

Synthesis of bio‐based polyurethanes from epoxidized soybean oil and isopropanolamine

Epoxidized soybean oil (ESO) and isopropanolamine were used to synthesize a new polyol mixture for preparation of bio‐based polyurethanes. The chemical synthetic route for reaction of ESO with isopropanolamine was analyzed by ¹H‐NMR. The results suggested that both ester groups and epoxy groups in ESO had reacted with amino group of isopropanolamine through simultaneous ring‐opening and amidation reactions. Epoxy groups in various situations exhibited different reactivity, and the unreacted epoxy groups were further opened by hydrochloric acid. The synthesized polyol mixture had high hydroxyl number of 317.0 mg KOH/g. A series of polyurethanes were prepared by curing the synthesized polyol mixture with 1,6‐diisocyanatohexance along with different amount of 1,3‐propanediol (PDO) as chain extender. Tensile tests showed that yield strengths of the polyurethanes ranged from 2.74 to 27.76 MPa depending on the content of PDO. Differential scanning calorimetry analysis displayed one glass transition temperature in the range of 24.4–28.7°C for all of the polyurethane samples, and one melt peak at high content of PDO. Thermogravimetric analysis showed that thermal degradations of the polyurethanes started at 240–255°C. In consideration of simple preparation process and renewable property of ESO, the bio‐based polyurethane would have wide range of applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and properties of zeroTrans soybean oil margarines

Experimental margarines were prepared in the pilot plant from interesterified soybean oil-soybean trisaturate blends and compared to a product made from hydrogenated soybean oil. Penetration, yield values, and water/oil off-data were determined. Margarine prepared from an interesterified soy-soy trisaturate blend (80:20) tended to crystallize slowly after votation and resulted in a somewhat harder than desirable product. However, addition of 20% liquid soybean oil to the interesterified oil yielded a softer product. The experimental products showed excellent oil and water loss properties under accelerated storage conditions.     

Mechanical and rheological properties of epoxidized soybean oil plasticized poly(lactic acid)

Poly(lactic acid) (PLA) is a well known biodegradable thermoplastic with excellent mechanical properties that is a product from renewable resources. However, the brittleness of PLA limits its general applications. Using epoxidized soybean oil (ESO) as a novel plasticizer of poly(lactic acid), the composite blend with the twin‐screw plastic extruder at five concentrations, 3, 6, 9, 12, and 15 wt %, respectively. Compared with pure PLA, all sets of blends show certain improvement of toughness to different extents. The concentration with 9 wt % ESO increases the elongation at break about 63%. The melt flow rates of these blends with respect to different ESO ratio have been examined using a melt flow indexer. Rheological behaviors about shear viscosity and melt strength analysis are discussed based on capillary rheology measurements. The tensile strength and melt strength of the blends with 6 wt % ESO simultaneity reach the maximums; whereas the elongation at break of the blends is the second highest level. ESO exhibits positive effect on both the elongation at break and melt strength. The results indicate that the blend obtained better rheological performance and melt strength. The content of 6 wt % ESO in PLA has been considered as a better balance of performance. The results have also demonstrated that there is a certain correlation between the performance in mechanical properties and melt rheological characterization for the PLA/ESO blends.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

PAO合成润滑油装置提高产品收率的对策研究

通过对PAO合成润滑油装置生产工艺现状的分析,对沉降脱渣-中和反应-过滤除渣的生产工序进行研究,确定了一步除渣工艺。结果表明,采用该工艺可以使PAO产品收率由82％提高至89％以上,同时简化了工艺,提高了效率。     

Frying stability of high-oleate and regular soybean oil blends

The objective of this work was to study the frying stability of soybean oil (SBO) with reduced linoleate (18∶2) and linolenate (18∶3) and elevated oleate (18∶1) contents. High-oleate SBO [HO SBO, 79% oleic acid (OA)] and a control (conventional SBO, 21.5% OA) were tested as is, as well as blended in different ratios to make three blended oils containing 36.9, 50.7, and 64.7% OA, abbreviated as 37%OA, 51%OA, and 65%OA, respectively. In addition, a low-linolenate (LL) SBO containing 1.4% 18∶3 and 25.3% 18∶1 was tested. Bread cubes (8.19 cm³) were fried in each of 18 oils (6 treatments×3 replicates). We hypothesized that stability indicators would be indirectly related to the total 18∶2 plus 18∶3 percentages and/or the calculated oxidizability. In general, the results were fairly predictable based on total 18∶2 and 18∶3 concentrations. The overall frying stability of the six oil treatments, from the best to the poorest, was: 79%OA, 65%OA, 51%OA, LL≥37%OA, and the control, with respective total compositions for 18∶2 plus 18∶3 of 10.3, 23.6, 36.3, 59.6, 48.9, and 62.8%. The greatly reduced concentration of 18∶3 in the LL SBO made it more stable than the 37%OA, even though the combined composition of 18∶2 and 18∶3 of LL was greater than that of the 37%OA. Blending conventional SBO with HO SBO had a profound effect on the oxidative stability index and color of the blended oils, but the values were not linearly predictable by the percentage of control in the blended oil. Other stability indices, including calculated oxidizability, calculated iodine value, conjugated dienoic acid value, and viscosity, changed in linear response to an increased proportion of the control in the blends.     

Effect of ultrasonic extrusion on properties of colloids and bio-based nanocomposites containing epoxidized soybean oil and nanoclay

Colloid prepared with epoxidized soybean oil (ESO) and a nanoclay, organically modified montmorillonite (OMMT), has been processed using an ultrasonic twin-screw extruder under various ultrasonic amplitudes and screw rotation speeds. Ultrasonic treatment has significantly increased OMMT dispersion in ESO, according to wide angle X-ray diffraction and rheological data. Yield stress, storage and loss modulus, and complex viscosity and relaxation time of the colloid have been increased with increase of ultrasonic amplitude. Under certain high ultrasonic amplitudes, the increase of one to two orders of magnitude in the above-mentioned properties of colloids has been observed. Creep and recoverable compliance have been decreased with the increase of ultrasonic amplitude. The tremendous changes in rheological properties of the colloid are a result of significantly improved OMMT dispersion with the aid of ultrasonic treatment. With no or low ultrasonic treatment, a higher screw rotation speed has improved OMMT dispersion since it brings more mixing effect. However, at high ultrasonic amplitudes, a higher rotation disrupts jet flow and has led to less dispersion improvement compared with the same colloid extruded at a lower rotation speed. Colloids extruded at 400 rpm were cured using triethylenetetramine to prepare bio-based nanocomposites. The nanocomposite prepared using colloid treated at 13 μm shows improved tensile strength and modulus compared with the nanocomposite prepared using untreated colloid.     

无硫酸环境环氧化大豆油合成条件优化

在无溶剂无硫酸条件下合成了环氧大豆油,对环氧化合成体系中的羧酸类型、用量及双氧水浓度等影响环氧值的若干因素进行了研究。甲酸的环氧化活性比乙酸和丙烯酸高。通过正交实验确定了最佳合成工艺条件为:m(大豆油)m(甲酸)m(双氧水)为1 0.15 1.0,反应温度60℃,反应时间5～6 h。产品环氧值≥6.20%,残留碘值<6.0%。产品经红外分析表明,在3008 cm-1处的原料C=C双键结构峰消失,在820 cm-1、787 cm-1处呈现出环氧键的伸缩振动的特征吸收峰。     

Water-blown rigid and flexible polyurethane foams containing epoxidized soybean oil triglycerides

Both rigid and flexible water-blown polyurethane foams were made by replacing 0–50% of Voranol® 490 for rigid foams and Voranol® 4701 for flexible foams in the B-side of foam formulation by epoxidized soybean oil. For rigid water-blown polyurethane foams, density, compressive strength, and thermal conductivity were measured. Although there were no significant changes in density, compressive strength decreased and thermal conductivity decreased first and then increased with increasing epoxidized soybean oil. For flexible water-blown polyurethane foams, density, 50% compression force deflection, 50% constant force deflection, and resilience of foams were measured. Density decreased first and then increased, no changes in 50% compression force deflection first and then increased, increasing 50% constant force deflection, and decreasing resilience with increase in epoxidized soybean oil. It appears that up to 20% of Voranol® 490 could be replaced by epoxidized soybean oil in rigid polyurethane foams. When replacing up to 20% of Voranol® 4701 by epoxidized soybean oil in flexible polyurethane foams, density and 50% compression deflection properties were similar or better than control, but resilience and 50% constant deflection compression properties were inferior. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

纳米粉体在冷冻机油的分散稳定性

在制冷系统中应用纳米材料是提高制冷机效率和可靠性的重要途径。将纳米材料应用到制冷系统中,需要将纳米粉体在冷冻机油或制冷剂中进行分散。总结了纳米粉体在冷冻机油中的分散稳定性的机理。分析了纳米粒子之间及纳米粒子与冷冻机油之间的作用势能与材质的Hamaker常数之间的关系,建立了冷冻机油中表面修饰后的纳米粒子之间作用势能的修正式,提出了纳米粉体基质材料的选择、粉体制备及其表面改性的原则。制备出纳米NiFe₂O₄冷冻机油,并通过吸光度/透光率随时间的变化考察了其稳定性。室温陈化140 d后,浓度为3 g·L^-1的纳米NiFe₂O₄冷冻机油的吸光度由3.124降为3.088,衰减幅度为1.15%。     

高分散稳定纳米金刚石润滑油的制备及其摩擦学性能

为了改善纳米金刚石颗粒(NDPs)在抗磨液压油(AHO)中的分散性,制备了酸氧化?高温热处理的NDPs (T-NDPs),将其与添加剂(油胺、聚异丁烯丁二酰亚胺T154和高碱值合成磺酸钙T106)混合后加入AHO中,制得含T-NDPs的AHO。用FESEM及Zeta电位仪、FT-IR和静态沉降法对其分散性进行表征,用四球摩擦磨损试验机、3D激光扫描显微镜和SEM/EDS对含T-NDPs的AHO的摩擦学性能和磨痕区域进行了分析。结果表明,酸氧化?高温热处理后,NDPs的平均粒径从270.2 nm降至153.5 nm,吸附添加剂后的T-NDPs的平均粒径为101.5 nm,添加剂可提高T-NDPs的油溶性并抑制其团聚,因而含T-NDPs的AHO具有良好的分散稳定性;T-NDPs含量为0.04wt%时,AHO的摩擦系数和磨斑直径比不加T-NDPs时分别降低13.2%和17.8%;T-NDPs作为润滑添加剂的减摩抗磨功效归因于其在摩擦界面起到支撑和滚动轴承的作用及在摩擦副表面参与润滑膜形成。     

Analysis of epoxidized soybean oil by gas chromatography

A fast and cost-effective procedure to quantitate epoxidized soybean oil by means of an external standard method is reported. This procedure is applicable to commercial epoxidized oils, polymer additive packages and polymers—polyvinyl chloride (PVC)—containing epoxidized oils. The epoxidized soybean oil is converted into fatty acid methyl esters with tetramethylammonium hydroxide, and analyzed by capillary gas chromatography with flame-ionization detection. In PVC samples, the epoxidized soybean oil was extracted with toluene and followed by derivatization prior to analysis. The methyl esters of monoepoxyoctadecanoic, diepoxyoctadecanoic and triepoxyoctadecanoic acid were separated with a short capillary column.