二甲基二烯丙基氯化铵-丙烯酰胺共聚物的合成与结构表征

用二步法合成了季铵盐阳离子单体N ,N 二甲基二烯丙基氯化铵 (DMDAAC)。第一步 ,向反应瓶中加入 1mol二甲胺的水溶液 ,控制温度 40℃以下 ,滴加 1mol氯丙烯和 1molNaOH水溶液 (其质量分数为 40 % )。滴加完后再反应 2h,分取上层有机相 ;第二步 ,将有机相加入反应瓶中 ,同时加入适量的丙酮 ,控制温度在 30℃以下 ,滴加 1mol氯丙烯 ,反应 4h。过滤、洗涤、干燥得阳离子单体DMDAAC ,总转化率为 63%。以n(DMDAAC)∶n(丙烯酸胺 ) =1∶3在水溶液中共聚 ,合成了阳离子共聚物 [P(DMDAAC AM) ]。反应以分别占单体总质量的 0 5 %的过硫酸钾和亚硫酸氢钠为引发剂 ,反应温度 40℃ ,反应时间 6～ 8h。并利用IR、1HNMR对单体和共聚物进行了结构表征。     

双烯丙基聚乙二醇的合成与表征

采用四丁基溴化铵作催化剂,由聚乙二醇（PEG）和烯丙基氯合成二烯丙基聚乙二醇,并用核磁共振^1（HNMR）、红外光谱对产物进行结构分析。研究了反应时间、反应温度、原料配比、催化剂用量、聚乙二醇相对分子质量对聚乙二醇封端率的影响。实验结果表明,最佳工艺条件为反应时间5h、反应温度60％、烯丙基氯用量为1.5、季铵盐催化剂用量为聚乙二醇物质的量比的5％,聚乙二醇封端率达到85％以上。     

Effect of third-phase properties on benzyl-n-butyl ether synthesis in phase transfer catalytic system

The production of benzyl-n-butyl ether from benzyl chloride and n-butanol is studied in phase transfer catalytic system. A third phase is formed when polyethylene glycol (PEG) and dodecane are used as the phase transfer catalyst (PTC) and an organic solvent, respectively. The production rate at the three-phase system is higher by seven times than that at the two-phase system. The ether production rate and its selectivity are dependent on the initial concentration of n-butanol. These are affected by the properties of the third phase, especially the concentrations of n-butanol and water in the third phase.

n-Butanol reacts with benzyl chloride and potassium hydroxide simultaneously. The reaction between n-butanol and potassium hydroxide occurs in the aqueous phase. Then, the selectivity of ether on a basis of initial n-butanol is below 0.6 in a stirred tank batch reactor. The selectivity is much improved at 0.9 by using a static triphase batch reactor in which the organic and aqueous phases are separated by the third phase. The interphase mass transfer can be accelerated by ultrasonic device.     

STUDY OF THE REACTION OF GLYCINE AND BENZOYL CHLORIDE UNDER INVERSE PHASE TRANSFER CATALYSIS

This study examined the feasibility of reacting benzoyl chloride (PhCOCl) and sodium glycinate (H₂NCH₂COOH) catalyzed by 4-dimethylaminopyridine (DMAP) in an alkaline (NaOH) aqueous solution/dichloromethane two-phase medium. This catalyzed reaction of benzoyl chloride and sodium glycinate was described by a pseudo-first-order rate law. The hydrolysis of benzoyl chloride in the two*phase reaction was neglected on the specified reaction conditions. In addition, the effects of operating conditions on the conversion of benzoyl chloride and the reaction rate. According to those results, the reaction rate decreases with an increasing concentration of benzoyl chloride, which contradicts the general rate law of reaction kinetics, This peculiar phenomenon could be accounted for altering the interfacial property due to the change of the chemical property of reactants and intermediate, and the interaction between reactants and intermediate which was transferred from organic phase to aqueous phase.     

PEG-400 Partitioning in the HCCD/PEG Process for Cs and Sr Recovery

Abstract

The properties of the chloro-protected cobalt bis(dicarbollide) anion in the acidic form (HCCD), and in the presence of polyethylene glycol (PEG-400), are well known for the recovery of Cs and Sr from acidic radioactive streams. In the early development of HCCD/PEG extraction processes, questions were raised regarding the ability to control the concentration of PEG-400 in the organic phase due to its high solubility in the aqueous process solutions relative to HCCD or the diluent. The purpose of this study was to quantify the partitioning behavior of PEG-400 under a wide variety of relevant process conditions. PEG distribution ratios (D _PEG ) were measured by equilibrium batch contacts between the organic and aqueous phases over a wide range of conditions using radiometric techniques with ¹⁴C labeled PEG-400 to monitor the behavior of the bulk material. The results vary dramatically from 0.1 < D_PEG < 50, indicate that the PEG phase transfer kinetics are rapid, and that the aqueous phase nitric acid concentration has minimal impact on PEG solubility. The molar concentration ratio of [HCCD]:[PEG] in the organic phase has the greatest impact on PEG solubility. This ratio should be maintained at [HCCD]:[PEG] greater than or equal to approximately 6 to minimize PEG losses from the organic phase.     

A LIMITATION OF REUSING THE CATALYST IN TRI-LIQUID-PHASE CATALYTIC SYSTEMS

This work demonstrates important factor influencing the reusability of the phase transfer catalyst in the third liquid phase in addition to the role of the possible loss of catalyst due to the dissolution of the catalyst into the aqueous and organic phases. When the catalyst might react with the byproducts, in addition to reacting with the organic substrate and aqueous nucleophile, it would lose its catalytic activity. The substitution reaction between the organic substrate and an aqueous nucleophile (sodium phenolate) with tetra-n-butylammonium bromide as a phase-transfer catalyst was employed as a model reaction and was performed in a batch reactor. Three organic substrates, including allyl bromide, n-butyl bromide, and ethyl 2-bromoisobutyrate, were tested. Each of the third liquid phases formed in these tri-liquid-phase catalytic systems was utilized three times to observe the change in the activity of the catalyst. The catalyst in the third liquid phase can be reused without any loss of its catalytic activity when allyl bromide or n-butyl bromide is utilized as the organic substrate; however, the catalytic activity declines when ethyl 2-bromoisobutyrate is the organic reactant. Therefore, the organic reactant plays a crucial role in determining whether the catalyst can be reused or not.     

A LIMITATION OF REUSING THE CATALYST IN TRI-LIQUID-PHASE CATALYTIC SYSTEMS

This work demonstrates important factor influencing the reusability of the phase transfer catalyst in the third liquid phase in addition to the role of the possible loss of catalyst due to the dissolution of the catalyst into the aqueous and organic phases. When the catalyst might react with the byproducts, in addition to reacting with the organic substrate and aqueous nucleophile, it would lose its catalytic activity. The substitution reaction between the organic substrate and an aqueous nucleophile (sodium phenolate) with tetra-n-butylammonium bromide as a phase-transfer catalyst was employed as a model reaction and was performed in a batch reactor. Three organic substrates, including allyl bromide, n-butyl bromide, and ethyl 2-bromoisobutyrate, were tested. Each of the third liquid phases formed in these tri-liquid-phase catalytic systems was utilized three times to observe the change in the activity of the catalyst. The catalyst in the third liquid phase can be reused without any loss of its catalytic activity when allyl bromide or n-butyl bromide is utilized as the organic substrate; however, the catalytic activity declines when ethyl 2-bromoisobutyrate is the organic reactant. Therefore, the organic reactant plays a crucial role in determining whether the catalyst can be reused or not.     

用198Au示踪法研究季铵盐体系萃取金

The solvent extraction of KAu(CN)2 from alkaline solution by quaternary ammonium salts (trialkylmethylammonium chloride or cetyltrimethylammonium bromide) waw investigated by means of ^198Au radioactive tracer method. Various parameters,such as the gold (I) concentration in aqueous phase,the modiffer,emulsifiation at the interface of two phases, and phase ratio used in the extraction of gold (I) were studied. The results demonstrate that almost all gold (I) in the aqueous phase was practically extracted into the organic phase. The water content in the organic phase decreased significantly with increase of gold (I) concentration using long chain alcohol as modifier,in contrast with the system with tributyl phosphate (TBP) as modifier. Emulsification at the interface of two phases decreases with an increase of modifier concentration in the organic phase or with the addition of a small amount of lysozyme into the aqueous phase. The method with ^198Au tracer can be directly used to determine the Au(I) concentration both in aqueous and organic phases, which is especially suitable for the low concentration of Au(I).     

Kinetics and extraction of phenol in phase-transfer catalyzed reaction

Under two-phase conditions, the feasibility of extracting/removing phenol from aqueous alkaline medium via reaction with allyl bromide dissolved in dichloromethane was investigated using phase-transfer catalysts in a stirred cell. The effects of the concentrations of base, reactant and catalyst, and temperature were also evaluated to obtain the optimum reaction conditions. According to these results, the extractive efficiency of phenolic substances varied strongly with increasing base concentration. The specific extraction rate, diffusivity, mass transfer coefficient and distribution coefficient of an intermediate product were determined to explain the reaction mechanism by the proposed theoretical model. During reaction, the concentration of the intermediate product in the organic phase was also measured, and a simulation method was used to examine the mass transfer behavior of the intermediate product in the liquid-liquid system.     

Extraction of Thallium with Butyl Acetate

ABSTRACT

Experimentally obtained extraction isotherms of the system thallium-sulfuric acid-sodium chloride-butyl acetate are presented. The influence of the sulfuric acid and chloride anion concentrations on the extraction equilibria of thallium was investigated. An increase in the acidity of the aqueous phase results in steeper extraction isotherms, and the amount of thallium extracted generally increases. The influence of chloride anions on the equilibrium is more complex. It was found that the extraction equilibria is not influenced by the chloride ion concentration, provided that the Cl/T1 ratio in the aqueous phase is ? 4. If this ratio is less than 4, the concentration of chloride anions significantly influences the extraction isotherms. The results obtained are discussed in terms of the composition of the complex in the organic phase. An apparent reaction constant equation is proposed for the prediction of the extraction equilibria.     

Linear polythioesters,XXVI. Products of interfacial polycondenation of bis(4-mercaptomethylphenyl)methane with some aliphatic and isomeric phthaloyl dichlorides

New polythioesters were synthesized by interfacial polycondensation of bis(4-mercaptomethylphenyl)methane with selected aliphatic and isomeric phthaloyl dichlorides. To determine optimum polycondensation conditions, the influence of the following factors on reduced viscosity and yield were studied: type of organic phase, concentration of hydrogen chloride acceptor (NaOH), concentration of reagents, aqueous/organic phase ratio, rate of acid chloride addition, reaction time and reaction temperature. A thorough examination was carried out only for the polycondensation of dithiol with adipoyl and isophthaloyl dichlorides chosen as model systems. The structures of polythioesters were confirmed by elemental analysis, X-ray analysis and infrared spectroscopy. Some physicochemical, mechanical and electrical properties were determined. The molecular weights were not measured, because of the low solubility of the obtained polythioesters.     

椰油丙基酰胺甜菜碱/聚乙二醇水溶液的分相研究

Phase separation behavior of cocamidopropyl betaine/water/polyethylene glycol (PEG) system was studied. The effects of concentration and molecular weight of PEG on the phase separation behavior were investigated. Clouding occurred when the con-centration of PEG was large enough in the betaine aqueous solution, and the concentration of PEG at cloud point decreased with the increase of PEG molecular weight for a constant betaine concentration. The bottom phase was the PEG-rich phase, and the upper phase was the betaine-rich phase. The volumetric ratio of PEG-rich phase to betaine-rich phase, at the same difference between the PEG concentration and the one at the cloud point, &#61508;Ccp (0.1 g&#8226;ml－1), decreased as the PEG molecular weight increased and approached 1 for higher PEG molecular weight (about 20000), which was similar to the typical aqueous two-phase system. This volumetric ratio depended on the initial PEG concentration, but independent of PEG molecular weight. The concentration ratio of betaine to PEG in both phases depended on the &#61508;Ccp, independent of PEG molecular weight.     

Exhaustive removal of anions from aqueous waste via nucleophilic displacement reactions in the presence of phase transfer catalysts

Nucleophilic anions such as phenoxide and cyanide dissolved in an aqueous phase were effectively reacted with alkyl halides present in an organic phase containing a phase transfer catalyst. Preliminary data show the concentration of these anions in water decreased from 10,000 ppm to less than 1 ppm in 2–3 h at less than 70 °C. This methodology enables treatment of hazardous anions that are difficult to remove when using a conventional approach.     

醋酸甲酯-甲醇-水体系的盐效应

在20℃的条件下研究了加入氯化钙对醋酸甲酯-甲醇-水体系产生的盐效应。实验结果表明,随着初始水相中氯化钙质量分数的增加,两相区逐渐扩大,醋酸甲酯在水相的溶解度和水在有机相中的溶解度均有所降低。在有机相中甲醇质量分数一定的条件下,随着初始水相中氯化钙质量分数的增加,甲醇在有机相和水相间的分配系数减小,甲醇的选择性系数而增大。这些结论表明,采用加盐萃取对醋酸甲酯和甲醇进行分离十分有利。对该含盐体系的液—液平衡数据采用Eisen-Joffe方程进行了关联,关联值与实验值的平均相对偏差为4 08%。     

Synthesis of cationic polyacrylamide by aqueous two‐phase polymerization in poly(ethylene glycol) chloride solution

Aqueous two‐phase copolymerization of acrylamide(AM) and acryloyloxyethyl trimethyl ammonium chloride (DAC) was performed in poly(ethylene glycol) (PEG) solution and in PEG chloride(Cl‐PEG) solution, respectively. Series of cationic polyacrylamide(CPAM) aqueous dispersion were prepared using potassium persulfate (KPS) as initiator. The effect of total amount of monomers, the dosage of initiator, the content of dispersant, the mass ratio of AM to DAC, and the temperature on the conversion, molecular weight, cationic degree, and stability of aqueous dispersion were studied in detail. It is found that the increase of initiator and reaction temperature resulted in the increase of the final conversion, whereas the increase of DAC and PEG concentration resulted in the decrease of the final conversion. The optimum reaction conditions of synthesis were as follows: (1) PEG‐H₂O system: PEG 7.5 g, AM 8 g, DAC 2 g, KPS 0.05 g, H₂O 100 mL, 70°C. In this process conditions, the molecular weight of CPAM was 3.21 × 10⁶, the cationic degree of CPAM was 24.4%, the storage stability of the aqueous dispersion was over 3 months. (2) Cl‐PEG‐H₂O system: Cl‐PEG 7.5 g, AM 8 g, DAC 2 g, KPS 0.05 g, H₂O 100 mL, 65°C. In this process conditions, the molecular weight was 3.68 × 10⁶, the cationic degree was 23.3%, and the storage stability of the aqueous dispersion was over 6 months. In general, the stability of CPAM aqueous dispersion in Cl‐PEG system is much better than in PEG system. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of n‐butyl phenyl ether by tri‐liquid‐phase catalysis using poly(ethylene glycol)‐600 as a catalyst – analysis of factors affecting the reaction in a batch reactor

As the second part of a series of studies on the synthesis of n‐butyl phenyl ether (ROPh) by tri‐liquid‐phase catalysis, this work examines the factors affecting the reaction between n‐butyl bromide (RBr, organic substrate) and sodium phenolate (NaOPh, aqueous nucleophile) with poly(ethylene glycol)‐600 (PEG‐600) as a phase‐transfer catalyst. The reaction is performed in a batch reactor at 45–85 °C for 2 h while the agitation speed is fixed at 1000 rpm. Experimental results indicate that the individual mole fractions of NaOPh and PEG‐600 slightly affect the reaction, while the total amount of these components exerts significant influence. When the mole fraction of PEG‐600 is 0.5, the reaction rate and the conversion of RBr are the highest. No byproducts are formed in the course of the reaction. The system using a non‐polar organic solvent might obtain a higher conversion compared with a weakly polar one owing to a higher concentration of PEG‐600 in the third liquid phase. Furthermore, adding NaOH facilitates the reaction to obtain a higher reaction rate than adding other kinds of salt because the addition of a base results in the formation of a third liquid phase. The catalytic ability of PEG with average molecular weight of 600 gmol^?1 is far higher than that with average molecular weight of 200, 400 and 1000 because PEG‐600 possesses an appropriate chain length which can tightly associate with Na⁺ to form the complex of PEG‐600‐Na⁺OPh^? for reacting with RBr. In addition, this nucleophilic substitution reaction is found to be pseudo‐first‐order with respect to RBr. © 2001 Society of Chemical Industry     

Extraction of cos dissolved in n-heptane into aqueous sodium hydroxide: Phase transfer catalysis

Extraction of COS, dissolved in n-heptane, into aqueous solutions of sodium hydroxide was studied in a 5 cm i.d. stirred cell. Extraction of COS is accompanied by fast reaction in the diffusion film. The role of phase transfer catalysts (PTC) in this uncommon example of industrial importance was studied by using tricaprylmethyl ammonium chloride (Aliquat-336), tetrabutyl ammonium chloride and cetyl trimethyl ammonium bromide as PTC.The specific rates of extraction were found to be first order in dissolved COS concentration and first order with respect to the PTC concentration in the organic phase. The maximum enhancement in the specific rate of extraction was found to be as high as about 25.     

Removal of Zinc Ions from Aqueous Chloride Solutions by Solvent Extraction Using Alamine 308

Abstract

A study has been undertaken to develop a solvent extraction system for zinc with Alamine 308 in aqueous chloride medium. The parameters investigated included reagent concentration, acid concentration, pH, aqueous to organic phase ratio, and rate of extraction and stripping. The study shows that zinc can be extracted rapidly and efficiently from aqueous chloride solutions. A number of aqueous stripping reagents removed more than 90% of the zinc from the organic phase with only one equilibration.     

Determination of Kinetics in Biphasic Recognition Chiral Extraction for Separation of Phenylsuccinic Acid Enantiomers

This paper reports on the determination of the intrinsic kinetics in biphasic recognition chiral extraction of phenylsuccinic acid enantiomers (H₂A) by L-IBTA and HP-β-CD in a modified Lewis cell. The two-phase homogeneous reaction model was selected, because there is a finite physical solubility of phenylsuccinic acid enantiomers in both the aqueous phase and the organic phase. The regime analysis was split up in three parts: a regime analysis on the aqueous phase reaction in the absence of organic phase reaction, a regime analysis of the organic phase reaction in the absence of the aqueous phase reaction, and a regime analysis of reactions in both phases. The reactions have been found to be first order with respect to H₂A and second order with respect to L-IBTA and HP-β-CD. Competitive extraction of H₂A enantiomers with HP-β-CD and L-IBTA has great influence on the extraction process. With increase of HP-β-CD concentration, high enantioselectivity was obtained, but the extraction rate decreases.     

Novel Gas-assisted Three-liquid-phase Extraction System for Simultaneous Separation and Concentration of Anthraquinones in Herbal Extract

abstract Gas-assisted three-liquid-phase extraction (GATE), which has the advantages of both three-liquid-phase extrac-tion and solvent sublation, is a novel separation technique for separation and con...