二乙酸亚碘酰苯及羟基对甲苯磺酰氧碘基苯的合成研究

通过碘化苯直接与 2 6 %～ 30 %的过氧化氢溶液和醋酸酐反应 ,合成了二乙酸亚碘酰苯 ,该反应避免直接使用较高浓度的过乙酸 ,且操作简单方便 ,产物收率较好 ,纯度高。同时也可不必分离出二乙酸亚碘酰苯直接加入对甲苯磺酸反应 ,得到羟基对甲苯磺酰氧碘基苯。     

Synthesis of Biodiesel from Soybean Oil using Heterogeneous KF/ZnO Catalyst

Biodiesel was produced by transesterification of soybean oil with methanol using ZnO loaded with KF as a solid base catalyst. It was found that the catalyst with 15 wt.% KF loading and calcined at 873 K showed the optimum activity. XRD, IR and Hammett indicator method were employed for the catalyst characterization. The results showed the activity of the catalysts was correlated with their basicity. The influence of various reaction variables on the conversion was also discussed.     

羰基化法合成氨基甲酸酯催化剂的研究进展

对氧化羰基化法、还原羰基化法及氧化还原羰基化法3种羰基化合成氨基甲酸酯方法中催化剂的研究进展进行了综述,其中着重讨论了各种配体及助剂对催化剂活性的影响。指出今后的研究应集中在寻找高效、价廉及可重复使用的催化体系或对高效的均相催化体系进行负载化以及研究多相催化体系的催化机理。     

Self-emulsifiable soybean oil phosphate ester polyols for low-VOC corrosion resistant coatings

A series of soybean oil phosphate ester polyols (SOPEP) was prepared by reaction of fully epoxidized soybean oil with phosphoric acid and simultanoeous hydrolysis in the presence of a polar solvent. The polyols were characterized by determination of acid value, oxirane number, hydroxyl value, molecular weight (GPC), and FTIR spectra. These polyols with varying amounts of acid phosphate groups could be self-emulsified to form aqueous dispersions after neutralization with organic base. These aqueous dispersion showed varying degrees of stability and their appearance ranged from opaque dispersions to translucent to clear solutions. Waterborne coating compositions were prepared using these aqueous dispersions as principal components and their thermally cured film properties were studied. it was found that by careful selection and formulation, SOPEPs can be successfully used for low-VOC waterborne coating formulations. SOPEPs with 3.5% phosphate ester content showed visibly superior corrosion resistance properties.     

三烷基氧膦络合萃取一元有机羧酸

络合萃取法对极性有机物稀溶液的分离具有高效性和高选择性。选择甲酸、乙酸、丙酸、丁酸为分离对象 ,三烷基氧膦 (TRPO)为络合剂 ,煤油为稀释剂 ,进行了系统的萃取相平衡实验 ,测定了络合剂浓度、稀释剂组成等因素对萃取平衡分配系数的影响。实验结果表明 ,溶质的亲油性对络合萃取平衡影响起主导作用 ;随TRPO浓度增大 ,萃取平衡分配系数呈增大趋势 ;随溶质初始浓度增大 ,有机相的溶质浓度向饱和萃取量接近 ;饱和萃取量随络合剂浓度的增大而增大。对相平衡分配系数进行拟合 ,精度令人满意。     

Transient testing of soy methyl ester fuels in an indirect injection,compression ignition engine

An evaluation of the exhaust emissions from a compression ignition engine for fuels composed of 100 and 30% methyl esters of soy oil (SME) is described. These fuels were compared with a low-sulfur, petroleum #2 diesel fuel in a Caterpillar 3304, prechamber, 75 kW diesel engine, operated over heavy- and light-duty transient test cycles developed by the United States Bureau of Mines. More than 60 h of testing was performed on each fuel. The objective was to determine the influence of the fuels upon diesel particulate matter (DPM) and gaseous emissions. The effect of a modern diesel oxidation catalyst (DOC) also was determined in an effort to minimize emissions. Neat SME produced a higher volatile fraction of the DPM, but much less carbon soot fraction, leading to overall DPM reductions of 23 to 30% for the light- and heavy-duty transients. The DOC further reduced the volatile fraction and the total DPM. The SME fuel reduced gaseous emissions of CO by 23% and hydrocarbons by over 30% without increasing NO_x. The DOC further reduced CO and hydrocarbon levels. Mutagenicity of the SME exhaust was low. Results indicate that SME fuel, used with a proper DOC, may be a feasible emission reduction technology for underground mines. References to specific products do not imply endorsement by the U.S. Bureau of Mines, a now defunct agency.     

Enzymatic production of alkyl esters through alcoholysis: A critical evaluation of lipases and alcohols

This paper focuses on a detailed evaluation of commercially available immobilized lipases and simple monohydric alcohols for the production of alkyl esters from sunflower oil by enzymatic alcoholysis. Six lipases were tested with seven alcohols, including straight and branched-chain primary and secondary alcohols. The reactions were conducted in a batch stirred reaction vessel using stoichiometric amounts of substrates under solvent-free conditions. Dramatic differences in alcoholysis performance were observed among the different lipases. For most of the alcohols, Novozym 435 produced the highest yield of FA alkyl esters, with yields well over 90% for methanol, absolute ethanol, and 1-propanol. Overall, 96% ethanol was the preferred alcohol for all lipases except Novozym 435, and ethanolysis reactions reached the maximal conversion efficiency. Increasing the water content in the system resulted in an increased degree of conversion for all lipases except Novozym 435. The secondary alcohol 2-propanol significantly reduced the alcoholysis reaction with all lipases; however, the branch-chain isobutanol was more advantageous than linear 1-butanol for Novozym 435, Lipozyme RMIM, and Lipase PS-C. Many commercial immobilized lipases are highly efficient and promising for the production of alkyl esters, offering high reaction yields and a simple operation process.     

The pseudo-single-phase,base-catalyzed transmethylation of soybean oil

The base-catalyzed transmethylation of soybean oil has been studied under conditions whereby the reaction starts as a single phase, but later becomes two phases as glycerol separates. Methanol/oil molar ratios of 6∶1 were used at 23°C. The catalysts were sodium hydroxide (0.5, 1.0, and 2.0 wt%), potassium hydroxide (1.0 and 1.4 wt%), and sodium methoxide (0.5, 1.0, and 1.35 wt%), all concentrations being with respect to the oil. Oxolane (tetrahydrofuran) was used to form a single reaction phase. The reactions deviated from homogeneous kinetics as glycerol separated, taking with it most of the catalyst. When 1.0 wt% sodium hydroxide was used, the methyl ester content reached 97.5 wt% after 4 h, compared with 85–90 wt% in the two-phase reaction. Sodium hydroxide (1.0 wt%), sodium methoxide (1.35 wt%), and potassium hydroxide (1.4 wt%) gave similar results, presumably because the same number of moles was used. The ASTM biodiesel specification for chemically bound glycerol was achieved after only 3 min when 2.0 wt% sodium hydroxide was used. However, the standard was not achieved after 4 h when 1.0 wt% sodium hydroxide was used, the MG content being 1.1–1.6 wt%. The use of 2.0 wt% catalyst is commercially impractical.     

Relationship between oxidative stability of vitamin E and production of fatty acids in oils during microwave heating

Effects of microwave heating on the oxidative stability ofd-tocopherols were studied in relation to the production of fatty acids in oils. During microwave heating, the stability of tocopherols decreased in the orderδ>β>γ>α. This order did not depend on the types of ethyl esters of fatty acids or oils present. But, the shorter the chainlength and the lower the degree of unsaturation of the fatty acid ethyl esters, the greater was the reduction in amount of individual tocopherols. A similar tendency was observed when tocopherol-stripped vegetable oils, with equimolar mixtures of tocopherols added, were treated under the same conditions. The reduction in tocopherols became greater with increasing levels of free fatty acids.     

Analysis of the polyethylene glycol glucosides and FA esters thereof by atmospheric-pressure ionization MS

Polyethylene glycol (PEG) glucosides (PEGG) and the PEGG esters of lauric acid were analyzed by atmospheric-pressure ionization MS (API-MS) with electrospray ionization. Straightforward mass characterization of the complex mixtures could be achieved without prior chromatographic separation. The constituents were identified on the basis of quasi-molecular ions. Individual components could be observed as protonated molecular ions [M+H]⁺ and/or as their NH₄ ⁺, Na⁺, or K⁺ adducts in positive ion mode. The mass spectrometric investigation showed that mixtures of PEGG consisted of monoglucoside, diglucoside, polyglucoside, and free PEG. The esterification product is a mixture of two types of nonionic surfactants: PEG-laurates and PEGG-laurates. The reasons for distortion of the quasi-molecular ion intensities and the stabilization of adduct ions were discussed. The rapid and highly sensitive API-MS analysis technique proposed here is well suited for direct characterization of complex mixtures and suitable for development as a routine analytical method.