二甲基硅油中溶剂挥发法制备微胶囊

以二甲基硅油(PDMS)作为连续相,用搅拌制乳——溶剂挥发的方法制备了聚丙烯腈(PAN)、醋酸纤维素(CA)、壳聚糖(CTS)等几种聚合物包覆Aliquat336(ALQ)、四甘醇(TEG)和牛血清白蛋白(BSA)等分离剂的微胶囊.其中挥发溶剂是N,N-二甲基甲酰胺(DMF),乙酸(AA)和水等极性溶剂.整个制备过程不需要添加任何其他表面活性剂,就可以得到分散性和球形度都很好的微胶囊,相比一般的溶剂挥发过程影响因素少,易于调控.制备得到的微胶囊表面致密,平均粒径在10～100μm之间.通过增加连续相粘度和降低聚合物溶液浓度的方法都可以使微胶囊粒径更小.在PDMS中添加一定量待包覆的萃取剂就可以实现对微胶囊包覆率的调控,实验中ALQ/PAN,TEG/CA和BSA/CTS微胶囊的包覆率分别可以达到0·43,0·38和0·08g/g.     

含P507微胶囊萃取水相中稀土的迁移行为

分别用乙基纤维素和海藻酸钙作为膜材，将Ｐ５０７（２－乙基己基鳞酸单２－乙基己基酯）微胶囊化。将这两种含萃取剂的微胶囊用于萃取Ｌａ３＋、Ｎｄ３＋和Ｌｕ３＋，可以将这些离子富集于微胶囊内。由于固体膜对芯材固定化和对离子的阻障作用，使萃取的传质过程发生了变化。以渗透系数来比较三种离子的传质速度，改变原料液的ｐＨ，可使离子的渗透系数改变，从而增大离子间渗透系数的差值。用６ｍｏｌＬ－１的ＨＣｌ对微胶囊内稀土离子进行反萃取，可以定量地富集稀土。     

微胶囊法对微量Pd（Ⅱ）萃取与洗脱的研究

微胶囊法对微量Ｐｄ（Ⅱ）萃取与洗脱的研究白光月，王玉洁，李永涛，张河哲（东北师范大学化学系，长春，１３００２４）毛北星（吉林省粮油专科学校，长春，１３００６２）关键词：微胶囊，钯的富集，三辛胺利用微胶囊膜对芯材的包埋性能，将油相萃取剂微胶囊化，使萃取...     

甲胺基阿维菌素苯甲酸盐微胶囊的制备与表征

以三聚氰胺-甲醛树脂为壁材,采用原位聚合法制备了甲胺基阿维菌素苯甲酸盐微胶囊,研究了三聚氰胺与甲醛的质量比、芯壁比、乳化剂、搅拌速度与时间、pH值、温度等因素对微胶囊形成的影响,对制备的微胶囊进行了表征,测定了甲维盐微胶囊化前后的光解率。结果表明,三聚氰胺与甲醛质量比为1∶2、芯材与壁材质量比为3∶2、以质量分数1%羟乙基纤维素(HEC)为乳化剂、在1000r/min搅拌速度下、pH=5.0和50℃保温2h可制备出形貌较好、平均粒径4.4μm的甲维盐微胶囊。红外光谱分析证明,甲维盐已完全被包覆在微胶囊中。紫外分光光度法测定其缓释性能良好。光解实验表明,微胶囊化可有效降低甲维盐原药的光解。     

用反相纸层析研究二(2-乙基己基)磷酸萃取稀土、铀(Ⅵ)、铜、钙、锌等离子的萃取机理

在前文中曾用反相纸层析研究了中性萃取剂磷酸三丁酯萃取铀酰离子的机理,并指出在纸上存在高沸点溶剂时可以测得准确的结果.现用酸性萃取剂二(2-乙基己基)磷酸(HDEHP)作为固定相进行反相纸层析.     

复凝聚法制备昆虫激素模拟物十二醇微胶囊及其释放性能

以明胶(GE)和阿拉伯胶(AG)为壁材, 通过复凝聚法将昆虫激素模拟物十二醇(C12OH)包覆在微胶囊中, 改变微胶囊壁材的浓度和交联度, 探讨了体系中C12OH的可控释放性能. 通过对壁材质量比为1及不同pH条件下的壁材凝聚率测试确定最佳复凝聚的pH为4.0; 考察了不同分散剂对微胶囊及其分散液性能的影响, 确定以Tween 20/Span 80(质量比1∶1)作为复凝聚法包覆C12OH体系的分散剂. 在壁材质量分数大于或等于3%条件下制备的微胶囊粒径大于壁材质量分数为2%的微胶囊, 胶囊的载药量和C12OH包覆率明显高于后者. 增加交联剂的用量, 壁材交联度、胶囊的载药量和C12OH包覆率都显著提高. 在相同用量的情况下, 用甲醛作交联剂时得到的微胶囊的交联度比用戊二醛作交联剂时的要低, 但其对C12OH的包覆率更高. 通过扫描电镜对微胶囊进行了分析, 认为GE与AG通过复凝聚能够将C12OH包覆在微胶囊内部. 对胶囊中C12OH在恒温恒湿条件下的释放研究结果表明, 3%与4%壁材含量下1%戊二醛交联的微胶囊和5%壁材含量下4%戊二醛交联的微胶囊中C12OH的释放行为有明显的可控性. 通过调节微胶囊的壁材含量和交联度可以达到昆虫激素可控释放的目的.     

改性胺微胶囊固化剂制备工艺的优化与性能

以改性胺1618固化剂为囊芯、脲醛树脂为壁材单体,采用界面聚合技术,成功制备了一种新型聚脲改性胺微胶囊固化剂。通过正交设计试验,考察了芯壁质量比、乳化剂种类和质量分数及搅拌速率对微胶囊包覆率、粒径大小及分布情况的影响,并确定了最佳制备工艺条件。采用马尔文激光粒度仪、扫描电镜对微胶囊粒径大小、分布情况及表面形貌进行表征,采用热重分析仪及傅里叶变换红外光谱对其化学结构进行表征,通过拉伸试验对自修复材料的断裂力学性能进行研究。结果表明,该微胶囊含有固化剂芯材,其热稳定温度为198°C,当芯壁质量比为0.7∶1、乳化剂为阿拉伯胶、乳化剂质量分数为1.5%、搅拌速率为800r/min时,所制备的微胶囊包覆率达到79.8%,平均粒径为207.5nm,呈规则的球形,分散性及表面致密性好。当基体材料中加入质量分数为1%的微胶囊后,拉伸强度提高64%,弹性模量提高287%。     

不同相对分子质量羟乙基纤维素对甲维盐微胶囊制备的影响

采用原位聚合法以三聚氰胺-甲醛树脂为壁材制备了甲维盐微胶囊。 探讨了不同黏均相对分子质量羟乙基纤维素作为乳化剂对微胶囊表面形貌、粒径及其分布、包覆率与载药量的影响,对使用不同黏均相对分子质量羟乙基纤维素作为乳化剂制备的微胶囊的释放性能进行了表征。 结果表明,以相对分子质量较小的羟乙基纤维素制备的微胶囊外形规则、致密且无黏连现象。 随羟乙基纤维素黏均相对分子质量的增加所得微胶囊的平均粒径及粒径分布逐渐增大,包覆率与载药量逐渐减小。 释放性能的研究表明,采用相对分子质量较小的羟乙基纤维素制备的微胶囊的释放性能较好。     

大豆分离蛋白-十二烷基硫酸钠微胶囊的制备与表征

以大豆分离蛋白(SPI)和十二烷基硫酸钠(SDS)为壁材, 以十六烷为芯材, 通过复凝聚法制备了微胶囊. 首先确定了SPI和SDS发生复凝聚的适宜pH、SPI/SDS配比、壁材浓度等. 在确定的实验条件下进行复凝聚, 凝聚物产率可达85%. 改变搅拌转速和芯壁比, 考察它们对微胶囊性能的影响. 用光学显微镜观察了微胶囊形貌. 用气相色谱测定了微胶囊的载药量和包覆率. 芯壁比为2、搅拌转速为400 r/min时所制备微胶囊的载药量可达61%. 随着芯壁比的增大, 微胶囊粒径及载药量都逐渐增大.     

在硫酸盐体系中用二-(2-乙基己基)磷酸萃取钴(Ⅱ)镁的研究

二-(2-乙基己基)磷酸是一种良好的萃取剂,对它的研究也较多。但用二-(2-乙基已基)磷酸萃取钴(Ⅱ)和镁的机理除了Baes作了些工作外,以后的工作就很少了。我们在前一工作的基础上又研究了二-(2-乙基已基)磷酸的煤油溶液从硫酸钠和硫酸铵溶液中萃取钴(Ⅱ)镁的萃取机理及介质、酸度、温度对萃取的影响。     

Effect of binary extractants and modifier–diluents systems on equilbria of propionic acid extraction

Propionic acid is an important carboxylic acid widely used in chemical industries. The recovery from aqueous waste streams and fermentation broth is of research interest. Extraction of carboxylic acids by reactive extraction using extractant-diluent, mixed extractants in diluents and extractants in mixed diluents etc. are emerging areas of study. With this aim reactive extraction of propionic acid was carried out to study: (i) effect of binary extractants (tri-n-octylamine(TOA):tri-n-butylphosphate (TBP), TOA:Aliquat 336 and TBP:Aliquat 336), (ii) effect of modifier (1-decanol) in different diluents (kerosene, n-octane, n-heptane, petroleum ether, butyl acetate, MIBK, 2-octanol, dodecanol, hexane) and (iii) effect of phase volume. Improved extractions using binary extractants and binary diluents were observed. Since liquid–liquid extraction is dependent on effect of modifier concentration, effect of phase volume, presence of single or binary extractants and binary diluents, the study will be useful in the design of reactive extraction process for propionic acid recovery.     

Extraction of catechol violet, chrome azurol S and eriochrome cyanine R with chloroform solutions of liquid anion-exchangers

The extraction of Catechol Violet, Chrome Azurol S and Eriochrome Cyanine R with chloroform solutions of tri-n-octylamine (TOA), TOA hydrochloride and Aliquat 336 has been investigated. From the extraction isotherms, absorption spectra of the organic phases and dependence of the extraction coefficients on extractant concentration, it was found that the singly-charged anions HL(-) are extracted preferentially, but acidic groups other than sulphonate can also form ion-pairs with alkylammonium cations at higher pH values of the aqueous phase, and at high acidity these dyes can be extracted other than by an anion-exchange reaction. The three dyes (especially Eriochrome Cyanine R and Chrome Azurol S) were strongly extracted with the liquid anion-exchanger used and Aliquat 336 was a better extractant than TOA or TOA hydrochloride. The absorption spectra for the organic phases containing Chrome Azurol S and Eriochrome Cyanine R depended on the extractant used.     

Separation of Zr from Hf in acidic chloride solutions by using TOPO and its mixture with other extractants

Liquid–liquid extraction of Zr and Hf from chloride solutions was performed by using TOPO extractant in kerosene. An effective extraction of Zr from Hf was achieved selectively at 2.5–3 M HCl condition. Moreover, a mixture of TOPO with DOS, D2EHPA, Aliquat 336, Alamine 336 and Alamine 308 were tested in order to investigate the extraction behavior of Zr and Hf. The mixture of TOPO and D2EHPA was found to increase the extraction of Zr and Hf. In the extraction by the mixture of TOPO and amine, the extraction percentage of Zr and Hf was decreased with the increase of amine concentration due to the preferential extraction of HCl. Finally, among the mixtures of TOPO and other extractants tested in this study, the TOPO alone system was found to be better for the mutual separation of Zr and Hf in hydrochloric acid media.     

Extraction of zirconium(IV) from HCl solutions by mixtures of Aliquat-336 and Alamine-336 with TBP

Synergism has been observed in the extraction of zirconium(IV) by mixtures of Aliquat 336 or Alamine 336 with a neutral donor TBP from aq. HCl solutions. Although the extractant dependency for Zr(IV) is found to be nearly second power with respect to TBP alone, monosolvate is found to be formed for extraction by its mixture with Aliquat 336 or Almine 336. Quantitative extraction is observed with mixtures at a lower acidity than that with individual extractants. The species formed is tentatively assigned to be Q₂ZrCl₆. TBP, where for Aliquat 336 and for Alamine 336.     

Cr(VI) ion removal from artificial waste water using supported liquid membrane

In this study, a novel flat-type synergic-supported liquid membrane was evaluated with a mixture of N-methyl-N,N,N-trioctylammonium chloride (Aliquat 336) and tributyl phosphate (TBP) as the carrier and kerosene as the diluent to remove Cr(VI) from synthetic waste water. The main parameters involved in the process were identified and optimised. The parameters were divided into two groups, those that were independent and those having an interaction. The parameters of the carrier/kerosene volumetric proportion and stirring rate were optimised individually due to their nature. The optimal values of these parameters were 0.5 and 500 min^?1, respectively, for a constant carrier/kerosene ratio and stirring rate in the designed experiments using the response surface method (RSM). The four parameters of TBP/Aliquat 336, chromium concentration in the feed phase, feed and product pH were optimised using RSM; it was observed that the TBP/Aliquat 336 ratio, feed pH, pH of the stripping phase and interaction of this parameter with feed concentration have the most important effects on the removal of Cr(VI). The optimal levels of these parameters were 0.61, 71.75 mg L^?1, 3.5 and 12.66 for the ratio of TBP/Aliquat 336, feed chromium concentration, pH of the feed and pH of the product, respectively. An experimental removal rate of 94.63 % at the optimized levels was obtained.     

Influence of operation conditions on the microencapsulation of PCMs by means of suspension-like polymerization

Microcapsules containing PRS® paraffin wax (core) and a polystyrene shell were prepared by suspension-like polymerization. The influence of reaction temperature, stirring rate, and mass ratio of paraffin wax to styrene on the properties of phase change materials microcapsules was studied. The reaction temperature had not a significant effect on the size of the microcapsules but an increase of molecular weight and a narrow molecular weight distribution of polystyrene shell were observed when reaction temperature was increased. An exponential relationship between the stirring rate and the mean particle diameter in number has been found. It was observed that paraffin is difficultly encapsulated when the paraffin/polymer mass ratio was higher than 2.00, as a consequence of a shortage of polymer that could not completely cover the amount of paraffin added. However, when a large proportion of monomer was employed, the polymer tended to polymerize inside the droplets during the microencapsulation process forming complex inner structures. The microcapsules obtained have an interesting energy storage capacity of 153.5 J/g that makes them suitable for different applications.     

Facilitated Cd(II) transport across CTA polymer inclusion membrane using anion (Aliquat 336) and cation (D2EHPA) metal carriers

PIMs have been involved as affinity membranes for recovery of metals (Cd, Pb, Zn) by facilitated transport from aqueous solutions under different speciation forms, either anionic or cationic. The motivation of this work is to compare the efficiency of the recovery process in the case of Cd(II) using extractants such as D2EHPA and Aliquat 336 that can form complexes with the cation Cd²⁺ or the anions CdCl₃⁻ and CdCl₄²⁻, respectively. The maximal Cd(II) recovery factors obtained in 8 h are 97.5% and 91.8% with D2EHPA and Aliquat 336, respectively. Although the transport fluxes with both carriers are not strongly different (ca. 2 μmol m⁻² s⁻¹), the recovery process in case of mixture of metals is better achieved with Aliquat 336. PIMs have shown a very good stability and a constancy of the transmembrane transport flux over 12 replicate measurements, each one lasting for 8 h repeated every 24 h.     

Synchronized extraction and purification of L-lactic acid from fermentation broth by emulsion liquid membrane technique

This study aims to investigate the recovery of L-lactic acid from fermentation broth by an emulsion liquid membrane (ELM), made up of sunflower oil as the diluent, Sorbitan monooleate (Span 80) as the surfactant, Aliquat 336 as the carrier, and sodium hydroxide (NaOH) solution as the internal aqueous phase. Particularly, the ELM process was properly set up, through the identification of the optimal ELM operating parameters on the final extraction efficiency of L-lactic acid, including Span 80 concentration, NaOH concentration, Aliquat 336 concentration, stirring speed, phase ratio, and treatment ratio. The obtained results showed that the extraction efficiency of L-lactic acid reached up to 99% under the following optimal conditions: 10 minutes after contact time, 4% w/w Span 80, 3% w/w Aliquat 336, 0.1?N solution of NaOH, stirring speed of 300?rpm, phase ratio 1, and treatment ratio 0.25. A stable system without considerable emulsion swelling and breakage was monitored using a dynamic light scattering (DLS) apparatus for the selected optimal ELM operating parameters.     

十八烷/聚(St-MMA)相变微胶囊制备及表征

采用乳液聚合的方法,分别选取聚苯乙烯(PS)、聚甲基丙烯酸甲酯(PMMA)或苯乙烯和甲基丙烯酸甲酯的共聚物为壁材,正十八烷为芯材,十二烷基苯磺酸钠(SDBS)为乳化剂,制作相变储能微胶囊。用粒径分析仪、透射电子显微镜(TEM)、热重分析仪(TG)和示差扫描量热测试仪(DSC)对微胶囊的形貌、相变热性能和热稳定性分别进行表征。结果表明:壁材选取两者共聚物,当两种单体的比例为St∶MMA=1∶5,SDBS用量为1.5g(总质量的3%)时,微胶囊粒径大小均匀,粒子分散性好,壁材的包裹性好。微胶囊的放热峰为起始温度为27.3℃,终止温度为31.9℃,相变温度为28.9℃,相变焓为48.4J/g。TG表明长期使用温度不能超过131℃。IR分析微胶囊中含有芯材和壁材。这种十八烷/聚(St-MMA)相变微胶囊可以用于诸能材料。     

Solvent extractions of zirconium and niobium from HCl solutions by Aliquat 336/Alamine 336 and DOSO mixtures

Liquid-liquid extractions of zirconium(IV) from aqueous HCl solutions by mixtures of Aliquat 336 or Alamine 336 and diocytl sulfoxide (DOSO) in the diluent benzene has been found to be always higher than that by any single extractant. While the cationic extractants extract Zr(IV) above 6M HCl, DOSO extracts from 4M onwards. Synergism has been observed in all cases. With any of these extractants extraction becomes almost quantitative at and above 10M HCl, but with mixtures of the cationic and neutral extractants, extraction is quantitative in the range 8–9M HCl. Although the extracted species with DOSO alone seems to be ZrCl₄·DOSO, with the mixture of extractants, however, the extracted species appear to be Q₂ZrCl₆·DOSO where Q is R₃ ⁺NH (for Alamine 336) and R₃ ⁺N(CH₃) (for Aliquat 336). Studies on separation of⁹⁵Zr–⁹⁵Nb pair from aqueous HCl media by Alamine 336 or DOSO and their mixtures in benzene exhibit preferential extraction of⁹⁵Nb leaving behind⁹⁵Zr in the aqueous phase, and extractions have been found to depend both upon the extractant and HCl concentrations.