Kinetics of the formation of symmetrical wax esters from the corresponding alcohols with the use of hydrobromic acid and hydrogen peroxide

The primary aliphatic alcohols n-octanol, n-decanol, and n-dodecanol have been converted to their corresponding symmetrical esters by using HBr and H₂O₂ in the absence of a solvent. The reaction was carried out at 30, 40, and 50°C and at mole ratios of alcohol to HBr of 1∶0.1, 1∶0.2, 1∶0.3, and 1∶0.5. The rate of the reaction was found to increase with increase in the reaction temperature and concentration of HBr. The maximal conversion of n-octanol was 72% at 40°C and a mole ratio of n-octanol to HBr of 1∶0.5. The kinetics of the reaction have been established, and the reaction was found to be first-order with respect to alcohol and bromine concentration in the organic phase, and second-order with respect to both. The second-order rate constants for n-octanol, n-decanol, and n-dodecanol are 27.08, 32.58, and 37.42 mL mol⁻¹ min⁻¹, respectively, at 40°C. The activation energy for the esterification reaction of n-octanol was found to be 16.32 kcal mol⁻¹.     

Some physical properties of castor oil esters and hydrogenated castor oil esters

Esters of castor oil and hydrogenated castor oil were prepared with C₆, C₁₂, C₁₆, C₁₈ fatty acids, using tetra‐n‐butyl titanate as a catalyst and n‐butyl benzene as a water entrainer. Physical properties such as melting point, refractive index, viscosity, and specific gravity of these esters were measured. Slip melting points of the esters were very low in both cases. These esters did not crystallize even at low temperature. The highest slip melting point obtained was 21 °C with stearoyl hydrogenated castor oil ester and lowest slip melting point obtained was —6 °C with hexanoyl castor oil ester.     

Enzymatic synthesis of wax esters from rapeseed fatty acid methyl esters and a fatty alcohol

Wax esters were transesterified from fatty acid methyl esters of rapeseed and a fatty alcohol (1-hexadecanol, 16:0). The amounts of both the substrates were fixed to 0.1 mmol and an immobilized enzyme, Lipozyme, was used as catalyst. The experiment was performed following a statistic central composite design with five variables. The enzyme/lipid ratio was varied between 0.3–0.9 of the substrate weight and the enzyme was equilibrated to different water activities varying from 0.11 to 0.44. A temperature range of 50–80°C was investigated and the reaction time lasted up to 40 min. A solvent, isooctane, constituted 0–30% of the substrate weight. The first experimental series was performed in small closed test tubes. In the second series the caps of the test tubes were off to evaporate the methanol produced during the reaction. The highest initial reaction rate was 9.6 g_{wax esters}/g_enzyme · h. It appeared when: the enzyme/lipid ratio was low, 0.3, the temperature was high, 80°C; no isooctane was present; and the water activity was below 0.11. The initial reaction rate was independent of the caps on the test tubes. With the large amount of enzyme the yield of wax esters was above 70% after 10 min in both experimental series. In the reaction with caps, the reaction reached equilibrium at 83% after 20 min at 80°C. However, without caps the continuous evaporation of methanol increased the equilibrium constantly, and after 40 min at 80°C a yield of 90% was reached.     

Physico‐chemical properties of palm olein fractions as a function of diglyceride content in the starting material

Crude olein preparations with different amounts of diacylglycerols (DAG) were refined, bleached and deodorized (RBD) prior to the dry fractionation process. The RBD olein samples with different amounts of DAG were then individually fractionated into low‐melting (super olein) and high‐melting fractions (soft stearin). Physical and chemical characteristics, i.e. iodine value, cloud point, slip melting point, triacylglycerol (TAG) and DAG profile, fatty acid composition, thermal profile and solid fat content, of the super olein and soft stearin fractions were analyzed. The TAG profile obtained from the RBD olein having a low DAG content (0.89%) showed a higher amount of the diunsaturated TAG, i.e. dioleyl pamitoyl glycerol, in the olein fraction (57.3%). This, consequently, led to super olein fractions with a better iodine value (IV 65) and the cloud point at 1.3 °C, compared to non‐treated super olein (DAG 5%) with an IV of 60.5 and the cloud point at 4.1 °C.     

Lipase-catalyzed synthesis of lesquerolic acid wax and diol esters and their properties

Lesquerolic acid was and α,Ω-diol esters were synthesized via immobilizedRhizomucor miehei lipase-(Lipozyme) catalyzed esterification of lesquerolic acid and alcoholysis of lesquerella oil. For each wax ester synthesis, when alcohol substrate was present at a slight (ca. 20%) stoichiometric excess and water content was kept low, over 94% of the hydroxy acyl groups were esterified. The extent of reaction and the ratio of monoester to diester produced for α,Ω-diol reactions was controlled by the solubility of diol in the medium. This latter quantity increased as alcoholysis proceeded due to the formation of partial glycerides and monoesters, which increased the polarity of the medium. Alcoholysis reactions were significantly slower when the medium diol content was above saturation. As the diol chainlength increased, diol solubilization decreased, the ratio of monoester to diester decreased, and the extent of hydrolysis increased. Alcoholysis reactions involving either fatty alcohols or diols suffered from acyl migration, which lowered the purity of lesquerolic acid esters. Several lesquerolic acid esters, synthesized on a preparative scale and purified via column chromatography, were evaluated for their properties: density, viscosity, and melting point. Potential applications for lesquerolic acid esters are discussed.     

Organogelation of plant oils and hydrocarbons by long-chain saturated FA,fatty alcohols,wax esters,and dicarboxylic acids

Conversion of oils into gels generally involves altering the chemical characteristics of the liquid. We describe here the gelling of vegetable oils, essential oils, and hydrocarbons at ambient temperature, without changing the chemical characteristics of the liquids, using saturated FA having carbon chain lengths of 10 to 31. The gelling ability of the added FA increased linearly with their chain lengths. Structure-function studies demonstrated that the carboxyl group, position of an additional hydroxyl group, and acyl chain length played an important role in gelation. Long-chain saturated fatty alcohols, wax esters, and dicarboxylic acids also had the ability to gel plant oils and hydrocarbons.     

聚丙烯酸改性高固含量漆蜡乳液的制备及性能

以漆蜡为原料,制备高固含量的漆蜡乳液,并进一步采用聚丙烯酸改性对高固含量的漆蜡乳液进行改性。以乳液固含量、离心稳定性和黏度为考察指标,研究引发剂用量、温度、时间和乳化剂用量对乳液性能的影响。采用四因素四水平的正交实验设计优化聚丙烯酸改性改性漆蜡乳液的工艺条件。结果表明,在引发剂用量0.3%、温度90℃、乳化时间300min、乳化剂用量10%的条件下,聚丙烯酸改性高固含量漆蜡乳液的固含量为60%,黏度为38500mPa·s,离心稳定性为1级。     

Enzymatic preparation of ricinoleic acid esters of long-chain monohydric alcohols and properties of the esters

Apart from the conventional chemical esterification process, long-chain alkyl ricinoleates also can be prepared by enzymatic esterification or by enzymatic alcoholysis with high yield and without undesirable side reactions. On sulfonation to the hydroxyl group, the alkyl ricinoleates produce surface-active compounds. The tetradecyl ricinoleate shows the best surface-active behavior and seems to be much better than that of sulfonated castor oil commonly known as “Turkey Red Oil”.     

利用NIRS和RI技术测试石油流体析蜡温度新方法

析蜡温度是重要的石油流体性质参数,得到准确的析蜡温度是保证含蜡原油管道安全输送的前提。提出了近红外光谱温度扫描测试法和折射率测试法,改进了近红外光谱波长扫描测试法,并从可靠性、灵敏性和稳定性等方面与常用的偏光显微镜法和差示扫描量热法进行比较。结果表明,近红外光谱法和折射率法可以得到可靠的测试结果,并具有较高的灵敏性和稳定性;实验操作和数据分析方法简单,测试结果不易受到制样过程影响,尤其适合挥发性较强的油样。此外,近红外光谱法测试时油样处于运动状态,可有效减小过冷度的影响,但与实际管输条件仍存在一定差别。     

过氧化钨酸-过氧化氢化学聚合法合成掺杂态聚苯胺

在过氧化钨酸-过氧化氢均相催化氧化体系中,在盐酸或对甲基苯磺酸的存在下合成出掺杂态聚苯胺(PANI/HCl和PANI/TSA)。反应终了后,加入碘化钾除去体系中剩余的过氧化氢。产物分离过程中,使用了抽滤法与甲苯-水共沸蒸馏法两种方法。与抽滤法相比,用共沸蒸馏法处理反应后的产物能得到高产率的掺杂态聚苯胺。使用傅立叶红外吸收光谱(FTIR)和紫外-可见光吸收光谱(UV-vis)研究了两种掺杂态聚苯胺的化学构造变化。使用四端子法测定了掺杂态聚苯胺的导电性能,其导电率能达到10-3S/cm数量级。     

Low-temperature properties of alkyl esters of tallow and grease

The low-temperature properties of mono-alkyl esters derived from tallow and recycled greases were determined for neat esters and 20% ester blends in No. 2 low-sulfur diesel fuel. Properties studied included cloud point, pour point, cold filter plugging point, low-temperature flow test, crystallization onset temperature, and kinematic viscosity. Compositional properties of the alkyl esters determined included water, residual free fatty acids, and free glycerol content. In general, the secondary alkyl esters of tallow showed significantly improved cold-temperature properties over the normal tallow alkyl ester derivatives. The low-temperature flow test did not show a 1:1 correlation with cloud point as previously observed with methyl soyate and methyl tallowate. For the homologous series methyl to n-butyl tallowate, ethyl tallowate had the best broad-spectrum low-temperature properties, both neat and when blended in diesel fuel. For the greases studied, both the normal and branched alkyl ester derivatives showed improved properties over corresponding tallow esters, especially with neat esters.     

Enzymatic direct synthesis of acrylic acid esters of mono‐ and disaccharides

BACKGROUND: There is an increased need to replace materials derived from fossil sources by renewables. Sugar‐cane derived carbohydrates are very abundant in Brazil and are the cheapest sugars available in the market, with more than 400 million tons of sugarcane processed in the year 2007. The objective of this work was to study the preparation of sugar acrylates from free sugars and free acrylic acid, thus avoiding the previous preparation of protected sugar derivatives, such as glycosides, or activated acrylates, such as vinyl acrylate. RESULTS: Lipase catalyzed esterification of three mono‐ and two disaccharides with acrylic acid, in the presence or absence of molecular sieves was investigated. The reactions were monitored by high‐performance liquid chromatography (HPLC) and the products were analyzed by matrix‐assisted laser desorption ionization–time of flight (MALDI‐TOF) mass spectrometry. The main products are mono‐ and diacrylates, while higher esters are formed as minor products. The highest conversion to sugar acrylates was observed for the D ‐glucose and D ‐fructose, followed by D ‐xylose and D ‐maltose. Molecular sieves had no pronounced effect on the conversion CONCLUSIONS: A feasible method is described to produce and to characterize sugar acrylates, including those containing more than two acrylate groups. The process for production of these higher esters could potentially be optimized further to produce molecules for cross‐linking in acrylate polymerization and other applications. The direct enzymatic esterification of free carbohydrates with acrylic acid is unprecedented. Copyright © 2008 Society of Chemical Industry     

Synthesis and characterization of synthetic lubricants based on dibasic acid

Synthetic esters have long been used in a variety of applications due to their excellent thermal stability, excellent cleanliness, natural lubricity, and polarity. In the present work, we aimed to prepare some synthetic base oils through preparation of different dibasic esters by esterification of dicarboxylic acids (adipic acid and azelaic acid) with different linear alcohols (hexanol, octanol, and decanol) and branched alcohol (2-ethyl hexanol) at 120°C. The reaction yield ranges between 85% and 94%. Fourier-transform infrared spectroscopy (FT-IR) and proton nuclear magnetic resonance (¹H-NMR) spectroscopy were used to analyze the structures of the produced compounds. Using thermo gravimetric analysis (TGA), the heat stability of the produced esters was determined, and it was found that the prepared esters have high thermal stability. The degradation of the prepared esters takes place in the range between 300 and 600°C. The rheological behaviour of prepared esters shows Newtonian behaviours, which means that Newtonian fluids obey viscosity Newton's law. The viscosity is independent of the shear rate. The results showed that the lubricity properties, based on their pour point, flash point, and oxidation stability of the esters, were significantly affected by the linear and branched alcohols used. There is a slight increase in kinematic viscosity and viscosity index values with decreasing the internal chain length of the dibasic acid. The esters which were based on adipic acid such as C₁ exhibited maximum values of VI: 187 compared to those which were based on azelaic acid such as F₁ with VI: 182. Viscosity and viscosity index increases with increasing the number of carbon atoms of the used mono-ol alcohols. Using branched alcohols gave almost the same viscosity results compared to using linear alcohol with the same number of carbons. Almost all prepared esters give pour point results ≤ −30°C.     

Solvent extraction of ethanol from aqueous solutions using biobased oils, alcohols, and esters

Distribution coefficients and separation factors were determined for the partitioning of ethanol and water from aqueous mixtures into several vegetable oils and their fatty alcohol and fatty ester derivatives. Castor oil, ricinoleyl alcohol, and methyl ricinoleate all show higher ethanol distribution coefficients, and similar or reduced separation factors, relative to other oils and derivatives studied here or reported by others. Of particular interest, ricinoleyl alcohol has an ethanol distribution coefficient 50% higher than that of oleyl alcohol, a commonly studied solvent for ethanol extraction from fermentation broths.     

Separation of stigmasta-3,5-diene, squalene lsomers, and wax esters from olive oils by single high-performance liquid chromatography run

To ascertain the authenticity of olive oils, the European Community Regulation requires the stigmasta-3,5-diene and wax ester contents to be determined. The official methods are time-consuming and not suitable for many daily analyses, as quality-control laboratories need. A method is presented here that allows single high-performance liquid chromatography separation of stigmasta-3,5-diene and wax esters, as well as of the squalene isomers, which give further information on the oil’s authenticity. For stigmasta-3,5-diene, the comparison with results obtained with the official method is good. Also for wax esters, the agreement was good, even if they were compared with results obtained from a quicker method as reliable as the official one. The possibility of separating the squalene isomers also at the same time makes the proposed method more advantageous. On the whole, the method, which is suggested for routine and quick screening but not for the exact evaluation of the analyte contents, seems to be a convenient choice for ascertaining on a daily basis the samples’ legal compliance (i.e., whether the analyte content is or is not below the legal value).     

Thermo‐mechanical properties of candelilla wax and dotriacontane organogels in safflower oil

The thermo‐mechanical properties of organogels developed by a complex mixture of n‐alkanes present in candelilla wax (CW) were investigated and compared with the ones of organogels developed by a pure n‐alkane, dotriacontane (C₃₂). In both cases, the liquid phase used was safflower oil high in triolein (SFO) and the variables studied were two levels of gelator concentration (1 and 3%), cooling rates of 1 and 10 °C/min, and two gel setting temperatures, 5 and 25 °C (T_set). Based on comparisons of the organogels made with C₃₂, the presence of minor molecular components in CW had a profound effect on the crystal habit of the n‐alkanes in CW‐based organogels, and therefore on their physical properties. Thus, independent of the cooling rate and T_set, C₃₂ showed a higher solubility and higher self‐assembly capability in the SFO than CW. Nevertheless, for the same gelator concentration and time‐temperature conditions, C₃₂ organogels had lower G' profiles than CW organogels. Additionally, independent of the type of gelator, more stable organogel structures were developed at T_set = 5 °C and using the lower cooling rate. The rheological behavior of the organogels was explained considering the formation of a rotator phase by the n‐alkanes, its solid‐solid transition, and their dependence as a function of the cooling rate and T_set. The results here obtained showed that it is possible to gelate SFO through organogelation with CW and without the use of trans fats.     

Mechanical properties of uncrosslinked and crosslinked linear low‐density polyethylene/wax blends

The mechanical properties of uncrosslinked and crosslinked linear low‐density polyethylene (LLDPE)/wax blends were investigated, using differential scanning calorimetry (DSC), tensile testing, and melt flow indexing. A decrease in the degree of crystallinity, as determined from the DSC melting enthalpies, was observed with an increase in the dicumyl peroxide (DCP) concentration. The Young's modulus increased with increased wax portions, and there was a higher increase for crosslinked blends. The yield stress generally decreased with increased peroxide content. Crosslinking caused an increase in elongation at yield, but increased wax content caused a decrease in elongation at yield. The stress at break generally increased with increasing peroxide content, but it decreased with increased wax content. The elongation at break decreased with an increase in the DCP concentration. Melt flow rate measurements indicated a mutual miscibility in LLDPE/wax blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 973–980, 2001     

Synthesis and properties of organosoluble polyimides derived from 2,2′‐dibromo‐ and 2,2′,6,6′‐tetrabromo‐4,4′‐oxydianilines

Two new aromatic diamines, 2,2′‐dibromo‐4,4′‐oxydianiline (DB‐ODA 4 ) and 2,2′,6,6′‐tetrabromo‐4,4′‐oxydianiline (TB‐ODA 5 ), have been synthesized by oxidation, bromination, and reduction of 4,4′‐oxydianiline (4,4′‐ODA). Novel polyimides 6a–f and 7a–f were prepared by reacting DB‐ODA ( 4 ) and TB‐ODA ( 5 ) with several dianhydrides by one‐step method, respectively. The inherent viscosities of these polyimides ranged from 0.31 to 0.99 dL/g (0.5 g/dL, in NMP at 30°C). These polyimides showed enhanced solubilities compared to those derived from 4,4′‐oxydianiline and corresponding dianhydrides. Especially, polyimides 7a , derived from rigid PMDA and TB‐ODA ( 5 ) can also be soluble in THF, DMF, DMAc, DMSO, and NMP. These polyimides also exhibited good thermal stability. Their glass transition temperatures measured by thermal mechanical analysis (TMA) ranged from 251 to 328°C. When the same dianhydrides were used, polyimides 7 containing four bromide substituents had higher glass transition temperatures than polyimides 6 containing two bromide substituents. The effects of incorporating more polarizable bromides on the refractive indices of polyimides were also investigated. The average refractive indices (n_av) measured at 633 nm were from 1.6088 to 1.7072, and the in‐plane/out‐of‐plane birefringences (Δn) were from 0.0098 to 0.0445. It was found that the refractive indices are slightly higher when polyimides contain more bromides. However, this effect is not very obvious. It might be due to loose chain packing resulted from bromide substituents at the 2,2′ and 2,2′,6,6′ positions of the oxydiphenylene moieties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Kinematic viscosity of fatty acid methyl esters: Prediction, calculated viscosity contribution of esters with unavailable data, and carbon–oxygen equivalents

Many properties of biodiesel, the mono-alkyl esters of vegetable oils, animal fats or other triacylglycerol-containing feedstocks, are largely determined by its major components, the fatty acid alkyl esters. Therefore, information on the properties of individual components and their interaction is essential to understanding and predicting the properties of biodiesel fuels. Viscosity, which affects flow and combustion of a fuel, is such a property. In previous literature, the effect of the structure of fatty esters on viscosity was discussed. However, these data are largely confined to esters with an even number of carbon atoms in the chain and that are liquid at 40 °C. To gain a better understanding of kinematic viscosity, this work additionally reports data on esters with an odd number of carbons in the fatty acid chain and some unsaturated fatty esters. Furthermore, the kinematic viscosity of some biodiesel fuels is affected by components that are solids at 40 °C. A method based on polynomial regression for determining the calculated viscosity contribution (CVC) of esters that are solid at 40 °C (saturated esters in the C₂₀–C₂₄ range) or esters that are liquids but not available in pure form is presented as these values are essential for predicting the kinematic viscosity of mixtures containing such esters. The kinematic viscosity data of esters are compared to those of aliphatic hydrocarbons in the C₆–C₁₈ range and those of dimethyl diesters. The increase of kinematic viscosity with increasing number of CH₂ groups in the chain is non-linear and depends on the terminal functional groups, chain length and double bonds. To illustrate this effect, carbon–oxygen equivalents (COE) are used in which the numbers of carbon and oxygen atoms are added. A straightforward equation, taking into account only the amounts and kinematic viscosity values of the individual neat components, suffices to predict the viscosity of mixtures of fatty esters (biodiesel) at a given temperature.