Cyanoethylation of hydroxy derivatives of fats

Mono-, di-, and trihydroxy derivatives of fats have been cyanoethylated in high yields by use of excess acrylonitrile as solvent and aqueous benzyltrimethylammonium hydroxide as catalyst. Reaction variables of the cyanoethylation in excess acrylonitrile have been examined with methyl 12-hydroxystearate as the model compound. At moderate reaction temperatures the cyanoethylation reaction is 93% complete before the competing polymerization of the acrylonitrile consumes the catalyst. Presented at the AOCS Meeting, New Orleans, May 1967. E. Utiliz. Res. Dev. Div., ARS, USDA.     

Cyanoethylation of Hydroxyethyl Cellulose: Preparation and Characterization

Commercial hydroxyethyl cellulose (HEC) was cyanoethylated with acrylonitrile in nonaqueous medium in the presence of sodium hydroxide under a variety of conditions. Variables studied included the amount of acrylonitrile and the reaction temperature. The reaction was proved by NMR and its extent was measured by determining the nitrogen content. The physical properties of the obtained derivatives—i.e., the electric properties and the apparent viscosity at various rates of shear—were investigated. It was found that the extent of reaction was increased by increasing the amount of acrylonitrile as well as the reaction temperature. The products were water soluble and their apparent viscosity increased with increasing nitrogen content. The same holds true for the dielectric constant and dielectric loss.     

Cyanoethylation of alcohols over solid base catalysts

Cyanoethylation of alcohols with acrylonitrile to form 3-alkoxypropanenitriles proceeds effectively over solid base catalysts such as alkaline metal oxides and hydroxides, lanthanum oxide, and alumina supported potassium fluoride and hydroxide at a reaction temperature below 323 K. The order of the reactivity of alcohols varied with the types of catalyst. With magnesium hydroxide and calcium hydroxide, the reactivity of alcohol decreased: methanol>ethanol>2-propanol, while with the alkaline earth oxides, lanthanum oxide, and alumina supported KOH and KF, the reactivity order was opposite. The reactivity orders are interpreted by the acidity of alcohol combined with the basic strength of the catalysts. The catalytic activity of solid base catalysts were scarcely affected by exposure of the catalyst to air before use for the reaction.     

Chemical modification of starch. II. Cyanoethylation

Rice starch was cyanoethylated by reacting it with acrylonitrile in presence of sodium hydroxide at different concentrations of acrylonitrile and various reaction temperatures. The effect of cyanoethylation on the rheological and solubility properties of starch was examined. It was found that the extent of the cyanoethylation reaction [expressed as %N and degree of substitution (DS)] increased by increasing acrylonitrile concentration provided that the latter was not less than 8 ml acrylonitrile per 10 g starch. A temperature of 50°C constituted the optimal temperature for the cyanoethylation of starch under the conditions studied. Examination of the rheological properties of the modified starch revealed that regardless of the DS, cyanoethylated starches are characterized by pseudoplastic behavior of particular interest were the results of the viscosity. Cyanoethylated starch having smaller amounts of cyanoethyl groups had higher viscosity than those of relatively larger amounts. On the other hand, the cyanoethylated starches were soluble in water regardless of the extent of cyanoethylation.     

微波辐射作用下氰乙基化木材的制备

利用微波辐射对杉木进行氰乙基化改性,研究了各种反应条件对氰乙基化反应的影响。并用红外光谱对氰乙基化木材进行了初步表征。结果表明,2 g杉木粉用KSCN饱和低浓度NaOH浸渍60 min,丙烯腈17 mL,温度在40~50℃下,微波辐射20~60 m in,(实际反应时间为80~120 min),辐射功率用650 W的30%,可获得与传统的恒温水浴反应240 min同样增重50%~60%的氰乙基化木材,但前者可缩短50%的反应时间。     

Vinyl ketostearates. Preparation,properties, infrared spectra,and analysis of 4- and 12-ketostearates

Summary Vinyl 12-ketostearate and vinyl 4-ketostearate were prepared by vinylating 12-ketostearic and 4-ketostearic acids, respectively, with vinyl acetate in the presence of a mercuric sulfate catalyst. The crude vinyl esters were purified by extracting the free fatty acids with dilute potassium carbonate, removing the mercury by distillation, and crystallizing successively from acetone and pertroleum ether. Infrared analyses revealed that lactonization occurred with the 4-ketostearic acid during the hydrogenation of the oiticica oil and during the vinylation of the keto acid. Two γ-lactones were produced. The γ-lactone of 4-hydroxy-2-octadecenoic acid was isolated in relatively pure form, and evidence was obtained for the concurrent formation of the less stable γ-lactone of 4-hydroxy-3-octadecenoic acid. The infrared spectra of the methyl keto esters, keto acids, vinyl keto esters, and the γ-lactone of 4-hydroxy-2-octadecenoic acid were determined in carbon tetrachloride solutions. It was found that the characteristic absorbances for the lactone-carbonyl, ester-carbonyl, ketonecarbonyl, and the vinyl group at about 5.6, 5.7, 5.8, and 6.1 microns, respectively, obey the Lambert-Beer law over a wide range of concentrations. Presented at the 33rd fall meeting, American Oil Chemists’ Society, Los Angeles, Calif., September 28–30, 1959. One of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Reactions with 3,5-pyrazolidinediones. III. Cyanoethylation of Some 4-Arylazo Derivates of 3,5-Pyrazolidinediones and 3-amino-2-pyrazolin-5-ones

4-Arylazo-3,5-pyrazolidinediones 1 react with acrylonitrile to yield either 4-arylazo-1-β-cyanoethyl-3,5-pyrazolidinediones 2 or 4-arylazo-1,2-di-β-cyanoethyl-3,5-pyrazolidinediones 3 depending on the reaction conditions. Hydrolysis of 2 and 3 affords the corresponding acids 4 and 5 . Treatment of 4-arylhydrazono-3-amino-2-pyrazolin-5-ones 6 with acrylonitrile affords either the mono-β-cyanoethyl derivatives 7 or the pyrazolopyrimidine derivatives 10 depending on the reaction conditions.     

生物油的成分分析及物性测定

以添加FeCl2的ZnCl2-KCl混合熔盐裂解纤维素和秸秆,制得生物油。采用傅立叶变换红外光谱法和气相色谱-质谱法分析生物油的成分。结果表明,生物油中成分复杂,含有氧元素、多种有机化合物,主要包括酮类、醛类、酚类及羧酸类等。测定了20～80℃生物油的密度和粘度,发现生物油的密度与温度呈较好线性关系,而生物油的粘度均大于水的粘度,且不同熔盐体系对秸秆生物油的粘度无较大影响。     

Process of acceleration of filtration of viscose

Conclusions It is significant that the purification on a single passage of viscose through porous ceramic corresponds to the result of a two-stage filtration of it in industrial filter-presses with standard fillings.Kiev Combine. Kiev Technological Institute of Light Industry. Translated from Khimicheskie Volokna, No. 3, pp. 20–22, May–June, 1969.     

乙烯酮(双乙烯酮)下游产品废水的治理技术

乙烯酮(双乙烯酮)是十分重要的化工中间体,其下游产品较多。江苏某化工厂开发生产乙烯酮(双乙烯酮)下游产品三十多个,年生产规模三万多吨,是国内以乙烯酮(双乙烯酮)为中间体生产精细化学品的综合骨干企业。针对乙烯酮(双乙烯酮)下游产品废水特点,该厂结合企业实际,开展了产品优化,结构调整,清洁生产,资源循环利用,节水降耗等工作,从源头削减了污染物的生产。同时投资二千多万元新建预处理装置三套,6000m3/d废水生化处理装置一套,使全厂乙烯酮(双乙烯酮)下游产品的废水得到了有效的治理。     

Effect of degree of deacetylation of chitosan on the kinetics of ultrasonic degradation of chitosan

The objective of the study was to explore the effect of the degree of deacetylation (DD) of the chitosan used on the degradation rate and rate constant during ultrasonic degradation. Chitin was extracted from red shrimp process waste. Four different DD chitosans were prepared from chitin by alkali deacetylation. Those chitosans were degraded by ultrasonic radiation to different molecular weights. Changes of the molecular weight were determined by light scattering, and data of molecular weight changes were used to calculate the degradation rate and rate constant. The results were as follows: The molecular weight of chitosans decreased with an increasing ultrasonication time. The curves of the molecular weight versus the ultrasonication time were broken at 1‐h treatment. The degradation rate and rate constant of sonolysis decreased with an increasing ultrasonication time. This may be because the chances of being attacked by the cavitation energy increased with an increasing molecular weight species and may be because smaller molecular weight species have shorter relaxation times and, thus, can alleviate the sonication stress easier. However, the degradation rate and rate constant of sonolysis increased with an increasing DD of the chitosan used. This may be because the flexibilitier molecules of higher DD chitosans are more susceptible to the shear force of elongation flow generated by the cavitation field or due to the bond energy difference of acetamido and β‐1,4‐glucoside linkage or hydrogen bonds. Breakage of the β‐1,4‐glucoside linkage will result in lower molecular weight and an increasing reaction rate and rate constant. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3526–3531, 2003     

Approximation of temperature dependence of the modulus of elasticity of glass

A refined nonlinear value of the main parameter of a material, i.e., the elongation modulus versus the instant temperature value, was suggested for introduction into the computational algorithm of tempering stresses.     

粉煤灰中烧失量检测的不确定度分析

以F类粉煤灰为例,详细介绍了测定粉煤灰中烧失量的步骤、计算数学模型、影响测量不确定度的因素以及各项测量不确定度分量评定,人员、设备、材料、方法、环境都是影响测量不确定的因素。     

A study of miscibility of blends of polybutadienes of varying microstructure

The miscibility of various amorphous polybutadienes with mixed microstructures of 1,4 addition units (cis, 1,4 and trans 1,4) and 1,2 addition units have been investigated. The studies here involved optical transparency, differential scanning calorimetry, and small angle light scattering. It was found that a 90 percent (cis) 1, 4 addition polybutadiene was immiscible with high (91 percent) 1,2 addition polybutadiene. Reduction of the 1,2 content to 71 percent induced an upper critical solution temperature (UCST) with the cis 1,4 polymer. Polybutadienes with 50 percent and 10 percent 1,2 contents were miscible above the crystalline melting temperature of the cis 1,4 polybutadiene. Immiscibility of the 91 percent 1,2 addition polymer was also found with a 10 percent 1,2 polybutadiene. The latter polymer also exhibits an UCST with the 71 percent 1,2 polymer. The results are used to interpret the characteristics of blends of polybutadienes of varying microstructure.     

几种乙炔加压设备性能的比较

阐述并比较了几种加压设备在乙炔加压清净过程中的性能和特点。