Absorption of carbon dioxide into non-aqueous solutions ofN-methyldiethanolamine

The chemical absorption rate of carbon dioxide was measured in non-aqueous solvents, which dissolved N-methyldiethanoamine (MDEA), such as methanol, ethanol, n-propanol, n-butanol, ethylene glycol, propylene glycol, and propylene carbonate, and water at 298 K and 101.3 kPa using a semi-batch stirred tank with a plane gas-liquid interface. The overall reaction rate constant obtained from the measured rate of absorption of carbon dioxide under the condition of fast pseudo-first-order reaction regime was used to get the apparent reaction rate constant, which yields the second-order reaction rate constant and the reaction order of the overall reaction. There was approximately linear dependence of the logarithm of the rate constant for the overall second-order reaction on the solubility parameter of the solvent. In non-aqueous solutions of (MDEA), dissolved carbon dioxide is expected to react with solvated (MDEA) to produce an ion pair.     

Mechanistic insights into the selective hydrogenation of resorcinol to 1,3-cyclohexanedione over Pd/rGO catalyst through DFT calculation

In our previous work, graphene-supported Pd catalyst (Pd/rGO) exhibited higher activity and selectivity for the liquid phase selective hydrogenation of resorcinol to 1,3-cyclohexanedione compared with other catalysts. In the present study, further experimental and theoretical investigations were conducted to reveal the reaction mechanism and the catalytic mechanism of Pd/rGO for resorcinol hydrogenation. The effects of graphene nanosheet and the solvent on the reaction were investigated, and the pathway for resorcinol hydrogenation was proposed supported by density functional theory (DFT) calculations. The results showed that the excellent selectivity of Pd/rGO to 1,3-cyclohexanedione was attributed to the strong π–π and p–π interactions between the graphene nanosheet and the benzene ring as well as hydroxyl in resorcinol molecule, which was in agreement with our previous speculation. In weak polar aprotic solvents, solvation free energy had less impact to the π–π and p–π interactions mentioned above. In strong polar aprotic solvents and polar protic solvents, however, the influence of solvation free energy was much greater, which led to the decrease in the conversion of resorcinol and the selectivity to 1,3-cyclohexanedione.     

溶剂对丁腈橡胶溶解、尺寸、结构和催化加氢的影响研究

丁腈橡胶（NBR）是由丁二烯和丙烯腈共聚而制得的一种重要的合成橡胶,而由NBR选择性加氢制得的氢化丁腈橡胶（HNBR）,不仅保持了NBR原有的耐油和耐磨性,其耐侯性、耐臭氧性等均得到极大改善,被广泛用于武器部件、航天用密封件等领域,是不饱和聚合物化学改性领域的一个重要研究课题。本文采用纳米粒度仪、乌氏黏度计、傅里叶变换红外等表征手段,结合密度泛函理论计算（DFT）,系统研究了溶剂性质对NBR在溶剂中的溶解行为、尺寸分布、分子结构及催化加氢性能等的影响。实验结果表明强亲电子溶剂不能溶解NBR,给电子溶剂及部分弱亲电子溶剂能较好地溶解NBR,特别是在酮类溶剂中,NBR粒径小且分布集中。DFT结果表明相比于气相氛围,在所有溶剂氛围中NBR链段里双键的键长均有所增长,且随着溶剂的极性增加而呈增长的趋势,NBR的偶极矩也随着溶剂极性增加而增加。特别是在酮类溶剂中,受溶剂效应的影响NBR分子的HOMO轨道由分子边缘向分子内部移动,表明对链段内部CC双键可能产生积极的影响。加氢结果表明在给电子溶剂中的加氢效果均优于弱亲电子溶剂,但无论选择何种溶剂,对NBR中CC双键的加氢选择性均为100%。该研究为NBR非均相溶液加氢体系中溶剂的筛选提供了理论依据。     

Rx-COSMO-CAMPD: Enhancing Reactions by Integrated Computer-Aided Design of Solvents and Processes based on Quantum Chemistry

Solvents strongly affect reaction-based chemical processes. Process design, therefore, needs to integrate solvent design. For this purpose, the integrated computer-aided molecular and process design (CAMPD) method Rx-COSMO-CAMPD is proposed. It employs a hybrid optimization scheme combining a genetic algorithm to explore the molecular design space with gradient-based optimization of the process. To overcome limitations of molecular design based on group-contribution methods, reaction kinetics and thermodynamic properties are predicted using advanced quantum-chemical methods. Rx-COSMO-CAMPD is demonstrated in a case study of a carbamate-cleavage process where promising solvents are designed efficiently. The results show that the integrated solvent and process design with Rx-COSMO-CAMPD outperforms computer-aided molecular design without process optimization in the identification of solvents that enable optimal process performance.     

Solvent effects on esterification equilibria

Solvents are known to have strong impacts on the yields of equilibrium reactions. This work focuses on the thermodynamic investigation of these solvent effects on esterification reactions of acetic acid and propionic acid with ethanol. Esterification of acetic acid was performed in the solvents acetone, acetonitrile (ACN), dimethylformamide (DMF), and tetrahydrofurane as well as in mixtures thereof. ACN promotes the esterification of acetic acid, whereas it is strongly suppressed by DMF. The esterification of propionic acid was investigated with various reactant concentrations in acetone. The experimental equilibrium data in pure solvents and solvent mixtures were modeled using the thermodynamic equilibrium constant K_a and the reactant/product activity coefficients predicted by the perturbed chain‐statistical associating fluid theory (PC‐SAFT). For a given K_a, PC‐SAFT is able to predict the influence of the solvent and even solvent mixtures on the equilibrium concentrations of esterification in almost quantitative agreement with the experimental data. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3000–3011, 2015     

果糖/对甲基苯磺酸磺化炭催化合成芳香醛肟的研究

以果糖/对甲基苯磺酸磺化炭为催化剂,在水溶液中能高效、高选择性合成芳香醛肟。考察了催化剂用量及种类、溶剂种类和反应温度等因素对反应产率的影响,研究了不同结构芳香醛底物对反应的容忍性,同时对催化剂的重复使用率进行了评价,并通过熔点测定和1H NMR等手段对产物结构进行表征。实验结果表明：m磺化炭∶m苯钾醛为0.1%,以水/甲醇（体积比5∶1）为溶剂,反应温度在100℃回流时,芳香醛肟的产率达到73%-97%。磺化炭在反应中具有良好的稳定性,重复使用3次,反应产率基本保持不变。该催化体系不仅对环境无污染,而且条件温和,反应时间短,效率高。     

溶剂化效应对金属-有机骨架材料界面微环境催化性能的影响

金属-有机骨架材料（metal-organic frameworks,MOFs）的纳微结构可根据特定需求进行功能化调控,有望成为良好的工业催化材料。由于溶剂环境可对其界面微环境及催化性能产生较大影响,因此研究溶剂化效应对于MOF材料的影响具有重要的意义。以Cu-BTC和MOP-15两种典型MOF材料作为研究对象,采用密度泛函理论与COSMO溶剂模型相结合的方法,考察了溶剂效应对材料几何结构与电子稳定性的影响,并研究了不同溶剂对其Lewis酸性的影响。结果表明,溶剂环境可以使材料中的电子从不饱和配位金属处转移到有机配体上,进而使材料具有更强的Lewis酸性,并且电负性较大有机配体构成的MOF材料,受溶剂效应的影响更加显著。本工作将有助于深入理解溶剂化对调控MOF材料液相催化活性的影响。     

Solvation models in the reaction between phenacyl bromide and 2-mercaptobenzimidazole

The reaction between phenacyl bromide and 2-mercaptobenzimidazole has been studied in 12 different protic and aprotic solvents. The kinetic study shows that the reaction is second-order with first-order dependence each on (phenacyl bromide) and (2-mercaptobenzimidazole). Analysis of rate data shows that there is no direct correlation between the rate constant and dielectric constant of the solvent. Correlation of rate data with different solvent parameters like hydrogen bond acceptor basicity, polarizability and solvent electrophilicity, using linear multiple regression analysis shows that the reaction is influenced by these properties of the solvent. From the regression coefficients, information on the mode of solvation of the reactants and the transition state is obtained. The reaction has also been studied at different temperatures and the thermodynamic parameters Δ H ^#, Δ S ^# and Δ G ^# are evaluated.     

磺化竹炭催化合成芳香醛肟的研究

以磺化竹炭为催化剂,芳香醛在水溶液中能高效、高选择性合成芳香醛肟。考察了催化剂用量及种类、溶剂种类和反应温度等因素对产率的影响,研究了不同结构底物对反应的容忍性,同时对催化剂的稳定性进行了评价,并通过熔点测定和1HNMR等手段对产物结构进行表征。实验结果表明:m(磺化竹炭)∶m(苯甲醛)为0.5%,以水/乙醇(体积比5∶1)为溶剂,反应温度在30℃时,芳香醛肟的产率达75%～95%。磺化竹炭在反应中具有良好的稳定性,重复使用5次,反应产率基本保持不变。该催化体系操作简便,反应时间短,收率高,并且对环境污染小。     

Alternative Bio-Based Solvents for Extraction of Fat and Oils: Solubility Prediction,Global Yield,Extraction Kinetics,Chemical Composition and Cost of Manufacturing

The present study was designed to evaluate the performance of alternative bio-based solvents, more especially 2-methyltetrahydrofuran, obtained from crop’s byproducts for the substitution of petroleum solvents such as hexane in the extraction of fat and oils for food (edible oil) and non-food (bio fuel) applications. First a solvent selection as well as an evaluation of the performance was made with Hansen Solubility Parameters and the COnductor-like Screening MOdel for Realistic Solvation (COSMO-RS) simulations. Experiments were performed on rapeseed oil extraction at laboratory and pilot plant scale for the determination of lipid yields, extraction kinetics, diffusion modeling, and complete lipid composition in term of fatty acids and micronutrients (sterols, tocopherols and tocotrienols). Finally, economic and energetic evaluations of the process were conducted to estimate the cost of manufacturing using 2-methyltetrahydrofuran (MeTHF) as alternative solvent compared to hexane as petroleum solvent.     

Solvolytic liquefaction of coals with a series of solvents

Solvolytic liquefaction of coals of different rank was studied with a variety of solvents at 370–390 °C under nitrogen in order to elucidate the role of solvent in coal liquefaction of this kind and to find a suitable solvent for the highest yields of liquefaction. The yield was found to depend strongly upon the nature of the coal as well as the solvent under these conditions. Pyrene and a SRC-BS pitch were excellent solvents for Miike coal, which was fusible with high fluidity at these temperatures. However, the former was less efficient for Itmann and Taiheiyō coals which were fusible at a higher temperature and non-fusible, respectively. The mechanism of solvolytic liquefaction is discussed, including nature of coal and solvent at reaction temperatures, in order to understand the properties required for high yields with non-fusible coals in solvolytic liquefaction. It is found that for liquefaction with a high yield if the coal is non-fusible, solvolytic reaction should take place between solvent and coal, so giving a liquid phase of low viscosity at the reaction temperature. The solvolytic reaction may be one of hydrogen transfer when SRC-BS is used as the solvent.     

γ-氯丙基三甲氧基硅烷季铵化反应规律探讨

探讨了γ-氯丙基三甲氧基硅烷与十八烷基二甲基叔胺季铵化反应中,无机碘化物与溶剂对反应速率的影响。通过定性分析反应中生成的白色沉淀以及拟合该反应速率常数,发现无机碘化物作为一种反应物参与了该季铵化反应,它与γ-氯丙基三甲氧基硅烷反应生成的高反应性γ-碘丙基三甲氧基硅烷加速了初期反应速率。在不同类型的溶剂中,该季铵化反应速率常数差别显著,一般来说反应速率随溶剂的介电常数越大而加快,但是苄醇偏离此规律比较远。并从热力学角度分析了溶剂对季铵化反应的影响。     

2-羟乙基吡啶的密度泛函理论研究以及溶剂化效应

以甲醛与2-甲基吡啶生成2-羟乙基吡啶为模型反应,采用密度泛函理论模拟计算了2-甲基吡啶与甲醛的反应机理,并用连续介质-类导体屏蔽模型(COSMO)研究了反应体系分别在不同溶剂中的溶剂化效应。通过分析确认了在水溶液条件下该体系的主要反应路径。     

Solvent polarity influences product selectivity of lipase-mediated esterification reactions in microaqueous media

Esterification reactions were evaluated by using lipases fromRhizomucor miehei (Lipozyme IM20) andPseudomonas cepacia (PS-30) with equimolar levels (1.77 mmol) of undecanoic acid and glycerol or 1,3-propanediol (1,3-PD) or 1,2-propanediol (1,2-PD) in organic solvents of log P (partition coefficient between 1-octanol/water) values of (−0.33–4.5. Reaction yields (percentage of esterified undercanoate) with glycerol ranged from 1.4 to 72%, with greatest yields observed in solvents of log P 4.0–4.5 for Lipozyme, whereas the PS-30 lipase was similarly effective (27–38% yield) over the full range of solvent polarities. For both enzymes, as solvent apolarity increased, so did the extent of acylation of glycerol in the final product mixture. Reaction yields with 1,3-PD ranged from 8.1 to 64% for Lipozyme and from 18 to 84% for PS-30 lipase, with greatest yields observed for both enzymes in solvents of log P values in the range 1.2–5.0. For both lipases, the shift to greater solvent apolarity was accompanied by an increased molar ratio of diacylated-1,3-PD/monoacylated-1,3-PD in the product mixture. Reaction yields with 1,2-PD ranged from 2.5 to 45% for Lipozyme and from 12 to 52% for PS-30 lipase, with greatest yields observed in solvents of log P values in the ranges 1.4–1.9 and 1.4–4.5, respectively. The shift to greater solvent apolarity was accompanied by an increased molar ratio of diacylated-1,2-PD: monoacylated-1,2-PD in the product mixture, except for Lipozyme in the three most apolar solvents (log P of 3.5–4.5) in which there was a general attenuation of activity. These results suggest the existence of a solvent polarity influence on reaction product selectivity in multiproduct reactions, which can be partially explained on the basis of differential solvation and extraction properties of solvents.     

Solvent Effects on High Temperature Polyimides and their Bonded Joints

Environmental stress crazing/cracking (ESCR/C) of adhesives under organic solvent exposure is a subject of great practical importance to adhesive end-users, especially in dealing with structural applications. In the past, the mechanical properties of several adhesive systems have been shown to degrade considerably after both prolonged and momentary exposure to solvents under a state of stress. In this study, the solvent resistance of three structural polyimide adhesives was studied, with respect to organic solvents that may come in contact with the adhesives during their service life. Initially, dog-bone samples of the resin systems were prepared, according to ASTM Standard D638-91a, and these were soaked in the solvents to obtain equilibrium solvent mass uptake curves. The solvents used in the study included acetone, methyl ethyl ketone (MEK) and ethylene glycol, among others. The equilibrated samples were then tested in a miniature tensile testing machine, to obtain stress-strain characteristics. Secondly, samples equilibrated in the solvents were held in a vacuum environment at 150°C (which is below the glass transition temperature of the adhesives) to desorb the solvent, and these were then tested to obtain residual properties. To study the durability of bonded joints under solvent exposure, Ti-6A1-4V/adhesive bonds were prepared and wedge tests were performed on them for periods up to several days in solvent baths. Based on the measured crack lengths, the strain energy release rate due to solvent-induced environmental stress cracking (G_ESC) was computed as a function of crack growth rate. The G_ESC measurements help quantify the durability of the bonded joints on exposure to the various solvents, and further help in ranking the adhesives in terms of solvent resistance.     

A highly regioselective synthesis of δ-lactones from meadowfoam fatty acids

Meadowfoam fatty acids, when treated with mineral acid catalysts in the presence of polar nonparticipating solvents, undergo a facile ring closure to form δ-lactones. Perchloric and sulfuric acids catalyze the cyclization at concentrations of 0.6–13 mole equivalents, both neat and in the presence of solvent. Under constant acid concentrations, methylene chloride was found to increase the rate of reaction, the regioselectivity for the formation of δ-lactone, and the overall yield. In the absence of solvent, increased acid concentration improved the yield of lactone but reduced regioselectivity for the δ-isomer. Solvent polarity plays a significant role in the regioselectivity of the cyclization for δ-lactone, with solvents of higher dielectric strength providing larger δ/γ ratios (38:1) and higher yields up to 92%.     

Experimental study on the coal tar hydrocracking process in supercritical solvents

In order to find the optimal operating parameters in high-temperature and low-temperature coal tar hydrocracking processes and to maximize the light oil yields, experimental studies have been carried out in a one-stage reactor in supercritical solvents. Xylene and gasoline were used as supercritical solvents to investigate their effects on the light oil yields. The results show that gasoline was more suitable as a supercritical solvent and that a suitable ratio of gasoline solvent to coal tar could result in higher light oil yields in both high- and low-temperature coal tar hydrocracking processes. The effects of different operating parameters, including temperature, hydrogen pressure, catalyst, and residence time, on light oil yield were tested. It was found that the yields of light oil from the two coal tar hydrocracking processes varied with the operating parameters in a similar manner. However, different values of the operating parameters gave rise to the maximum yields of light oil from the respective processes.     

A Mathematical Analysis of Membrane Separation Parameters for Liquid/Liquid Dialysis in Single or Multiple Stages

Abstract

The effects of membrane separation parameters using liquid/liquid dialysis under idealized conditions and using hollow fiber geometry were calculated with the aid of a computer. These calculations were carried out for both single stage and multiple stages. Membrane separation parameters include the intrinsic properties of the membrane, the nature of the dialysis solvents, the flow rates of both feed and solvent streams, and the dimension of the hollow fiber. It was concluded that an efficient process using liquid/liquid dialysis requires a membrane with a high intrinsic permeability constant and a reasonable separation factor, as small an inner radius of hollow fiber as is practical, and a dialysis solvent with an acceptable activity coefficient for the key species and a flow rate suitably coupled to that of the feed.     

Functional monomers and polymers, 116. Asymmetric addition of n-butyllithium to aldehydes by chiral polymers and related compounds containing dimethylamino bornanol moieties

Asymmetric addition reaction of n-butyllithium to aldehydes was studied by using chiral polystyrene derivatives and chiral low molecular model compounds, both of which were derived from cis,endo-3-dimethylamino-2-hydroxybornane. The higher optical yields were achieved by using low molecular model compounds, and particularly the highest value was obtained in the case when ether was used as the solvent. The effect of reaction temperature, sort of the solvents and the molar ratio of the reagent to aldehyde on the asymmetric addition was also discussed.