甲基氢氯硅烷合成工艺进展

简述和分析了甲基氢氯硅烷的主要合成工艺。格利雅法和再分配法由于成本高、产物分离困难和无法连续化生产,难以适应大规模的工业化生产;而直接法、裂解法和还原法因其成本低廉,产率高。便于连续化生产,具有工业实用价值。甲基氯硅烷还原法生产工艺可以将Rochow直接法中的副产品转变为高附加值的甲基氢氯硅烷,是一种可持续发展合成工艺。     

The peroxidic species generated by ozonolysis of oleic acid or methyl oleate in a carboxylic acid medium

The ozonolysis of oleic acid or methyl oleate in a carboxylic acid medium produces three major peroxidic species as well as aldehyde. These peroxidic compounds have been identified as 1-acyloxyalkyl-1-hydroperoxides, 1,2,4-trioxolanes, and bis(1-acyloxy-1-alkyl) peroxides. The bis(1-acyloxy-1-alkyl) peroxides have not been reported previously as oleic acid or methyl oleate ozonolysis products. A¹H nuclear magnetic resonance examination of the ozonization products of oleic acid or methyl oleate in carboxylic acids, as well as methanol and iso-octane, led to the identification of the peroxidic compounds and aldehyde.     

Development of a Solvent Process for the Dyeing of Wool Sliver

The development is described of a prototype machine for dyeing wool continuously in 75 % formic acid at 50–60d?C, with recovery of the formic acid by distillation. A complete plant for treating 8000 lb of wool per day of two shifts was estimated to cost $A120,000 (£55,000). Excluding the cost of dyes and further processing, dyeing wool on this scale of operation was estimated to cost 70 cents (7-7 d.)per lb, and at 200,000 lb per day with three-shift operation 5-3 cents (5–8 d.)per lb. The very even uptake of dye obtained in formic acid would be expected to result in further savings on the cost of recombing after dyeing.     

臭氧氧化法合成乙醛酸乙酯

以马来酸二乙酯为原料,乙酸乙酯作溶剂,采用臭氧氧化和加氢还原工艺合成了乙醛酸乙酯,获得的较佳工艺条件为:n(乙酸乙酯)∶n(马来酸二乙酯)=15∶1,臭氧化温度20℃,反应时间80 min;以Pd/C作催化剂,m(Pd/C)∶m(马来酸二乙酯)=0.09∶1,氢气压力4 MPa,还原温度25℃,还原时间5 h。在该条件下,马来酸二乙酯的转化率达100%,产物收率≥89.0%,产物色谱纯度≥96.6%。采用IR和1HNMR技术对产物结构进行了表征。     

Technical new feature

A continuous process for the commercial production of isopropenyl stearate (IPS) from triple pressed stearic acid and a stabilized form of propyne has been developed. Cost estimates, including capital costs, operating costs, and profitability, for commercial scale plant production which show the process to be economically feasible are presented. This potentially profitable process offers the advantages of reliable raw material sources, minimal external thermal requirements, and usable process waste streams. For a plant producing 5 million pounds of IPS per year, the selling price range is 80 to 107 cents/lb IPS, corresponding to a raw material cost range of 27 to 54 cents/lb of IPS. For a 20 million pound per year plant, the selling price range is 58 to 85 cents/lb IPS. The selling prices include a 20% annual return on fixed capital investment. Fixed capital requirement ranges from 2.7 to 10.9 million dollars (3rd quarter, 1975) for plants ranging in size from 5 to 50 million pounds of IPS per year, respectively.     

The influence of trace components on the melting point of methyl soyate

The objective of this study was to determine the effect of various amounts of unsaponifiables and bound glycerol on the crystallization temperatures of methyl soyate used as biodiesel. The preparation of methyl esters did not affect the amount of unsaponifiable matter in biodiesel. A synthetic unsaponifiable mixture added to distilled methyl soyate and blends of methyl soyate and No. 1 diesel fuel (20:80, vol/vol) did not affect the crystallization onset temperature, cloud point, or pour point at concentrations up to 3% by weight. The amounts of monoglycerides and diglycerides in methyl soyate decreased from 2.60 and 9.87%, respectively, to 0% as the methanol/soybean oil ratio increased from 90 to 200% of the theoretical requirement. Transesterification reactions conducted with less than 130% of the theoretical amount of methanol resulted in methyl soyate with a higher cloud point because of the presence of saturated mono- and diglycerides. Pure mono- and diglycerides added to distilled methyl soyate at 0 to 1.0% did not change the pour point of the esters, but the cloud point of esters increased with increasing amount of saturated mono- or diglyceride. Pure saturated mono- or diglyceride presented in concentrations as low as 0.1% increased the cloud point of methyl soyate. Similar results were obtained with mono- and diglyceride mixtures present in incompletely converted methyl soyate.     

Crude glycerol glucoside esters of cottonseed oil: Preliminary cost analysis

Glycerol glucoside esters prepared by transglycosylation of starch and glycerol, followed by interesterification with esters of cottonseed oil fatty acids, are well suited for use in the steadily growing food emulsifier market. They offer formulators and processors a wide range of compositions and physical properties for achieving more effective emulsification without increase in cost. Process flowsheets, capital costs, manufacturing costs, and general expenses are given for the production of 5.7 million pounds and 17.2 million pounds of crude glycerol glucoside esters annually in hypothetical 4-ton batch and 12-ton batch grass-roots plants, respectively. A material balance and preliminary plant layout for the 12-ton batch plant are also provided. The cost of crude esters ranges from 37.4 cents to 43.7 cents/lb, indicating that the crude esters would be competitive with many commercially available food emulsifiers. The process can be carried out in conventional batch process equipment without production of polluting byproducts. Fixed capital investment for a new 12-ton batch plant would be $2.5 million, and for a new 4-ton plant, $1.3 million.     

Reducing the crystallization temperature of biodiesel by winterizing methyl soyate

Methyl soyate, made from typical soybean varieties, has a crystallization onset temperature (T _co) of 3.7°C and, as a biodiesel fuel, is prone to crystallization of its high-melting saturated methyl esters at cold operating temperatures. Removal of saturated esters by winterization was assessed as a means of reducing theT _co of methyl soyate. Winterizing neat methyl esters of typical soybean oil produced aT _co of −7.1°C, but this was not an efficient way of removing saturated methyl esters because of the low yield (26%) of the separated liquid fraction. However, aT _co of −6.5°C with 86% yield was obtained by winterizing the neat methyl esters of a low-palmitate soybean oil; aT _co of −5.8°C with 77% yield was obtained by winterizing methyl esters of normal soybean oil diluted with hexane.     

Edible cottonseed flour by air classification of glanded seed: Cost analysis

A new, edible, 65%-protein cottonseed flour having the characteristics of flour produced from glandless cottonseed has been prepared from milled, hexane-extracted glanded cottonseed flakes by a simple, practical, economical air classification process. The product has physical and functional characteristics that make it attractive for use in food formulation and it meets the free gossypol standards of both the U.S. Food and Drug Administration and the Protein Advisory Group of the United Nations System. A process flowsheet and a material balance are given: capital costs, manufacturing costs, general expenses, profitability and selling prices are indicated for annual productions of up to 17.5 and 35 million lb of flour in hypothetical industrial-scale satellite plants having daily capacities of 25 and 50 tons of flour, respectively. It is estimated that fixed capital investment for a 25-ton/day plant would be $4.0 million, and for a 50-ton/day plant, $5.5 million. Production of edible flour from prime-quality cottonseed kernels would cost as little as 15.8 cents/lb and the selling price of flour, allowing for the value of coproducts, would be as low as 23.6, 18.9, and 16.5 cents/lb for payout periods of 2, 3 and 4 years, respectively. Selling price would be competitive with the price of soy protein concentrate over most of the production range studied. Presented at the AOCS Annual Meeting, 1981, New Orleans. One of the facilities of the Southern Region, Agricultural Research Service, U.S. Department of Agriculture.     

Ozonolysis of the Semicoking Tar of Coal from the Shubarkol Deposit

The results of studies on the determination of the effect of ozonization on the hydrofining of coal tar from the coal of the Shubarkol deposit are reported. It was established that preliminary ozonization for 60 min makes it possible to increase the total yield of liquid products by 44.8% in the subsequent catalytic hydrogenation conversion of tar (5 MPa, 450°C, and a pseudo-homogeneous Mo-containing catalyst) and to increase the yield of a fraction with boiling points to 180°C by 17.7%, as compared with their concentrations in the parent tar.     

对映选择性氢化法合成苯甘氨酸甲酯

以α 肟基苯乙酸甲酯为原料,硫酸奎宁为修饰剂,通过Pd/C催化氢化合成苯甘氨酸甲酯。考察了反应温度、溶剂、修饰剂的量对对映选择性的影响。最佳反应条件:25～28℃、乙醇为溶剂、氢气压力101 325kPa、n(修饰剂)∶n(底物)=1∶10,苯甘氨酸甲酯的光学产率达51 3%。     

环保型大豆油墨的制备

采用大豆油衍生物大豆油甲酯为溶剂,制备环保型大豆油墨,并与矿物油溶剂制备油墨的性能进行比较。试验结果表明:大豆油墨的总体性能与矿物油油墨相当,而在黏性、稳定性和光泽方面,大豆油墨更优于矿物油油墨。     

Alcohols from ozonolysis products of unsaturated fatty esters

1-Nonanol and alkyl 9-hydroxynonanoates were more readily prepared by hydrogenation of the respective isolated aldehydes than by direct hydrogenation of products from reductive ozonolysis of oleate esters. Hydrogenation with nickel catalysts and aprotic solvents reduced the isolated aldehydes in good yield with a minimum of side reactions. Although the noble metal catalyst and hydroxylic solvent systems frequently used in similar reductions were also effective, they required a promoter that fortuitously catalyzed hydrolysis of acetals that formed during hydrogenation. Direct hydrogenation of the ozonolysis products resulted in side reactions and a mixture of products difficult to separate. Presented in part at the AOCS meeting, Chicago, October 1967.     

Curing and mechanical characterization of a soy‐based epoxy resin system

A potentially inexpensive alternative epoxy resin system based on soybean oil has been developed for polymer composite applications. Epoxidized methyl soyate (EMS) and epoxidized allyl soyate (EAS) have been synthesized at the University of Missouri–Rolla. These materials consist of mixtures of epoxidized fatty acid esters. The epoxidized soy‐based resins provide better intermolecular crosslinking and yield materials that are stronger than materials obtained with commercially available epoxidized soybean oil (ESO). The curing behavior and glass transition have been monitored with differential scanning calorimetry. Neat resin test samples have been fabricated from resin systems containing various amounts of EMS, EAS, and ESO. Standardized tests have shown that the addition of EAS enhances the tensile and flexural properties of the base epoxy resin system. Therefore, epoxidized soy ester additives hold great potential for environmentally friendly and lower cost raw materials for the fabrication of epoxy composites for structural applications. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3513–3518, 2004     

异丁香酚连续臭氧化制备香兰素研究

以逆流操作高效丝网波纹填料气液反应塔用于异丁香酚连续氧化 ,明显优于间歇臭氧化反应。香兰素得率达 86.4 % ;臭氧基本耗净 ,单耗 0 .31。与间歇反应比较 ,两个关键指标均相差近一倍 ,而且生产能力大幅度提高 ,为异丁香酚法工艺路线的工业化提供依据     

Application of modified iron-containing catalysts and preliminary ozonization of coal from the Shubarkol deposit to the hydrogenation of this coal

The results of the hydrogenation processing of coal from the Shubarkol deposit in the presence of natural bauxites from the Turgai deposit in the Republic of Kazakhstan are reported. With the use of a sample of bauxite containing 23.7% Fe₂O₃ as a catalyst, a higher yield of liquid products (54.2%) was obtained, as compared with those on other bauxite samples (49.5–53.8%). It was established that the modification of catalysts containing iron with elemental sulfur additives (0.75–1.25%) makes it possible to increase the yield of liquid products to 62.3–67.3%. A positive role of the preliminary ozonization of coal, which makes it possible to increase the yield of total liquid products upon hydrogenation by 13.3% in comparison with the yield of liquid products obtained with the use of coal not treated with ozone, was demonstrated.     

Chemical Characterization and Physical Properties of Solvents Derived from Epoxidized Methyl Soyate

Reactions of epoxidized methyl soyate (EMS) with alcohols, carbon dioxide, and acetone yielded liquids with solvent properties that make them more suitable than methyl soyate for dissolving polar substances. The reactions of EMS in the presence of Amberlyst‐15 with alcohols, including methanol, ethanol, n‐butanol, and 2‐methoxyethanol, produced a series of solvents containing ether (–OR) and alcohol (–OH) groups. Reactions of EMS with carbon dioxide and acetone gave products with carbonate and ketonide functional groups, respectively. The complex mixture of compounds present in the product, EMS(MeOH), resulting from the reaction of EMS with MeOH, was characterized by MS and NMR investigations. In addition to products resulting from MeOH addition across the epoxide ring, were major amounts of cyclic tetrahydrofuran derivatives that were derived from reactions of methyl linoleate (18:2) with MeOH. All of the solvents were characterized by high boiling points and low vapor pressures. Their viscosities were higher than that of methyl soyate. Especially notable were their very high Kauri‐butanol values, which ranged from 280 to 852, all of which are much higher than that (57) of methyl soyate. Such high KB values indicate that these solvents have very favorable solubilizing properties, which is illustrated by the ability of EMS(MeOH) to readily dissolve both polar (e.g., MeOH) and non‐polar (e.g., hexane) compounds.     

Hyperbranched polyols from hydroformylated methyl soyate

Hydroformylation of methyl soyate produces a mixture of fatty acid methyl esters with zero, one, two, and three hydroxyl groups, the major component being with two hydoxyls (around 50%). Polymerization of methyl esters of hydroxy fatty acids gives a hyperbranched product with a different content of hydroxyl groups depending on the degree of conversion. Molecular weights can be controlled by controlling the degree of conversion but also using monofunctional components. A range of hyperbranched polyols with acceptable viscosities and functionalities, suitable for flexible applications, was obtained by stopping the reaction at varying degrees of conversion. Monte-Carlo simulation of the polymerization of hydroxylated methyl soyate gave molecular weights and polydispersity which were compared with experimental values. Although hydroxylated methyl soyate contains considerable amounts of mono- and difunctional fatty acids, the system produces a physical gel at the highest conversions. This is due to very high molecular weights and was confirmed by experiments and the simulation. The simulation unexpectedly gave lower molecular weights but wider distribution than the experiments. This discrepancy was explained by the combination of experimental difficulties and possible side reactions leading to higher molecular weights. Functionality of polyols determined from gel points at critical NCO/OH ratios was reasonably close to predictions. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Laboratory optimization of process variables in reductive ozonolysis of methyl soyate

The laboratory experiments for reductive ozonolysis of methyl soyate were divided into four statistically designed groups, according to ozonolysis medium (methanol or water) and ozone carrier gas (oxygen or air). Each group comprised 27 separate experiments, each a one-third replicate of a 3⁴ factorial. Significant independent variables were determined by a preliminary set of experiments. Besides ozonolysis medium (X) and carrier gas (Y), the following significant independent variables were studied: medium/ester ratio (A), reduction catalyst (B), reduction pressure by hydrogen (C), and reduction temperature (D). By gas-liquid partition chromatography of the dimethyl acetals of the two products, which included methyl azelaaldehydate (MAZDA) and pelargonic aldehyde (PDA), aldehyde yields were determined for each experiment in the statistical groups. Analysis of variance of the data (F-test) showed the following main effects and interactions for yield of MAZDA where oxygen carrier gas, water as the ozonolysis medium, and palladium-on-carbon catalyst were used for reduction: Y, YA, YB, YD, AD, BD, and AC. Data fit (regression analysis) provided regression equations. Computer solution of these equations indicated optimum process levels. Based on these optimum levels, the predicted over-all yield of MAZDA is 89% of theoretical. Presented in part at the AOCS Meeting, Philadelphia, October 1966.     

Defatted peanuts: Preliminary cost study

Defatted peanuts are high in protein and low in fat content. A preliminary cost study for defatting Virginia peanuts with hexane in three all-new hypothetical commerical plants indicates operating cost can be as low as 84 cents/lb of peanuts extracted when packaged in 502×308 tins. Cost in fully depreciated plants is as low as 61.5 cents for a volume of extracted peanuts equivalent to the amount of unextracted peanuts normally packaged in 502×308 tins. Process development shows promise for further reducing these costs which are based on limited exploratory pilot plant research. Presented at the Peanut Utilization Research Conference, Jan. 15–16, 1962, New Orleans, La. One of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U.S.D.A.