离子交换树脂在有机催化反应中的应用进展

介绍了离子交换树脂催化剂在酰基化、烷基化、酯化、醚化、醛酮缩合、异构化和低聚、环氧化和开环等有机合成反应中的应用进展;评述了离子交换树脂催化剂的催化性能和可回收利用性;展望了离子交换树脂类催化剂的未来发展方向。     

COMPLEXATION IN ION EXCHANGER PHASE. PROPERTIES AND APPLICATION OF ION EXCHANGER COMPLEXES

ABSTRACT

This paper reviews the properties of complex forming ion exchangers (CFIE) and those of the ion exchanger complexes (IEC) with transition metal ions. It is mainly dedicated to the development of a novel approach in characterizing IEC which is based on the consideration of CFIE as three-dimensional polymeric ligands. The approach is illustrated by the results obtained by studying the specificity of complex formation with CFIE of different types, the structure, properties and possible applications of IEC as anion exchangers, as electron exchangers, as ligand exchangers and some others. A particular attention is paid to the tailored synthesis of the IEC with desired properties such as the composition of the statistically-average coordination center, the distribution of metal ions along the polymer chain, etc., and to their application as catalysts which combine the high selectivity and activity of the homogenous metal-complex catalysts with the technological convenience of the heterogeneous ones. The application of the IEC as convenient models for bio-catalysts (metalloenzymes) is also discussed.     

Ion-Exchange Behavior of New and Novel Zirconium(IV)-Based Composite Cation-Exchangers

The synthesized polyaniline-Zr(IV) selenoiodate and polyaniline-Zr(IV) selenomolybdate composite ion exchangers were characterized by Fourier transform infrared spectroscopy, UV spectra, X-ray diffraction, scanning electron microscope, thermogravimetric analysis, and conductivity studies. The ion-exchange capacities, effect of eluent concentration, elution time, elution behavior, and pH on ion-exchange capacity were also studied to exploit the ion-exchange capability of the composites. The study revealed that polyaniline-Zr(IV) selenoiodate and polyaniline-Zr(IV) selenomolybdate ion exchangers are having excellent ion-exchange capacity values for K⁺ ion 1.36 and 1.44?meq?g^?1, respectively. The organic polymeric part of the composites provides mechanical and chemical stability, whereas the inorganic part supports the ion-exchange behavior and thermal stability. The increase in electrical conductivity is due to the inorganic and organic parts. A mechanism for the formation of the polyaniline-Zr(IV) selenoiodate and polyaniline-Zr(IV) selenomolybdate composite ion exchangers is discussed, which may also be applied for the preparation of other composite ion exchangers. Sorption behavior of metal ions on the composites was studied in different solvent systems. On the basis of distribution coefficient values (K_d), it has been found that the cation-exchange materials are highly selective for Pb(II)-ions. Such modified composite materials can be applied as an electrochemically switchable ion exchanger for water treatment, especially water softening.     

Synthesis and studies on core–shell type anion exchange resins based on a hybrid polymeric support

In pursuit for new materials for recovery of noble metals, novel anion exchangers, based on new type of core–shell polymeric supports have been synthesized. The designed matrices, with reactive chloromethyl groups concentrated on a surface of the polymeric base, the Amberlite XAD‐4 adsorbent, have been modified using ethylenediamine and polyethyleneimine. The obtained ion exchangers were employed in processes of sorption of gold, platinum, and palladium chlorocomplexes, then, they were compared to similar resins based on volumetric polymeric supports. The studies covered porosity measurements, determination of sorption behavior in the presence of counter ions as well as kinetic and column studies. Ultimately, an attempt to access a core–shell character of the resins has been made using digital‐optical microscopy. The proceeded analyses allowed to determine the localization of the resins’ functionalities and their advantages over traditional ion exchange resins. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43841.     

Syntheses and the Main Properties of Fiban Fibrous Ion Exchangers

The works on synthesis and main properties of fibrous ion exchangers are reviewed in the paper. The main attention is paid to the FIBAN materials found practical applications in water treatment and air purification processes. The following methods for preparation of ion exchange fibers have been considered: mechanical mixing of inert fiber‐forming polymer solutions or melts with finely dispersed ion‐exchangers with their following spinning into fibers; preparation of composite fibers containing polymeric reinforcement in the polyelectrolyte body; spinning of specially prepared polymers containing ionizable groups and having fiber‐forming properties; grafting of ionogenic polymers (or polymers in which ionogenic groups can be introduced after grafting) onto polymer chains of the existing polymer fiber; polymer analogues conversion of existing polymeric fibers by introducing in their structure ionizable functional groups. Conditions for preparation of ion exchange fibers with high exchange capacity, optimal swelling and acceptable mechanical properties have been outlined.     

New Ion Exchangers Based on Copolymers: 2,3-(2-Hydroxy-3-Methacryloyloxypropoxy)Naphthalene–Styrene

Synthesis and characterization of the new polymeric ion exchangers with thiol and sulfonyl hydroxide groups are presented. These new sorbents were also compared with polymeric microspheres possessing methylenethiol groups on the surface presented previously. The polymeric cation ion exchangers in the form of microspheres were obtained by the suspension-emulsion polymerization tetrafunctional monomer: 2,3-(2-hydroxy-3-methacryloyloxypropoxy)naphthalene (2,3-NAF.DM) with styrene (St). Next, multistage modification introducing sulfur-containing group (thiol or sulfonyl hydroxide or methylenethiol) on the surface of polymeric matrices was made. In order to obtain sulfonyl hydroxide derivatives the matrices were performed as follows: the parent microspheres were treated by H₂SO₄ (Method I) or with the addition of oleum (Method II). The thiol groups were introduced in a two-stage reaction. In the first stage chlorosulfonation of parent microspheres in the presence of chlorosulfonic acid was carried out. Finally, the reduction of modified microspheres by using SnCl₂·2H₂O was conducted. The sulfur group content (elemental analysis, scanning electron microscope EDX SEM), thermal properties (thermogravimetric analysis), porous structure as well as the swelling characteristics of the functional beads were examined. The surface texture was also visualized by the AFM method.     

Recent Developments in the Synthesis, Characterization and Applications of Zirconium(IV) Based Composite Ion Exchangers

This article provides a review in the area of zirconium(IV) based organic–inorganic composite ion exchange materials used in analytical, pharmaceutical and environmental protection processes. It focuses on the synthesis, characterization and electroanalytical applications of various Zr(IV)-based composite ion exchangers in detail. The results obtained in different studies have also been critically reviewed. Also reviewed are the various composite cation exchange materials used as electroactive materials for the fabrication of ion-selective membrane electrodes. The ion exchange kinetic parameters of Zr(IV) based composite ion exchangers have been discussed, which provide the preliminary idea before the selection of the material for a particular application.     

离子交换树脂催化酯化研究进展

与传统的无机催化剂相比,离子交换树脂表现出良好的催化性能并且能回收再利用。本文简单介绍了离子交换树脂的种类,重点介绍了离子交换树催化剂在酯化反应中的应用进展。     

烯烃聚合后过渡金属催化剂负载化研究进展

综述了后过渡金属催化剂负载化方式和载体的种类及其催化特性,该催化剂载体包括无机载体、聚合物载体、自固载和介孔分子筛等。通过与均相催化剂性能的比较,进一步阐述了负载的目的和必要性。随着这一领域研究深入,将对后过渡金属催化剂工业化发展具有重要的意义。     

Polymere Netzwerke als Träger

Historically ion exchangers are the oldest application of polymer networks as carriers. Electron exchange resins, polymerbound enzymes, Merrifield synthesis, polymeric reagents and immobilized microorganisms open nowadays a broad field of utilization. Of decisive importance for all these applications is the accessibility of these polymer fixed target groups. Gel permeation chromatography is a valuable tool to obtain information about swollen polymer networks and specially whether the pores are available from outside. The influence of reaction conditions on the structure of the network is described and the inherent problems are discussed with polymeric reagents as example.     

烷基二苯醚二磺酸盐的研究进展

介绍了表面活性剂烷基二苯醚二磺酸盐的合成、生产及应用情况。着重阐述了二苯醚Friedel-Crafts烷基化反应催化剂的研究进展、磺化的研究进展及产品应用领域的拓展情况。烷基化反应常用的催化剂是Lewis酸、负载型AlCl3、超强酸、杂多酸和离子液体,由1,3-烷基咪唑、烷基季铵盐和AlCl3制备的离子液体催化剂催化合成烷基二苯醚的反应时,产物收率高,无环境污染。     

MCM-41中孔分子筛的改性及其应用

综述了MCM—41中孔分子筛的合成方法,影响因素,重点介绍了儿种中孔分子筛改性方法,并强调了其有机改性。同时概述MCM—41在精细合成催化,分子吸附及分子组装方面的应用及发展状况,对其应用前景也作了相应分析。     

负载复合后过渡金属烯烃聚合催化剂研究进展

综述了负载和复合型后过渡金属烯烃聚合催化剂的研究进展。把后过渡金属催化剂负载化,可以适合现有工业生产的工艺要求,改善聚合物产品的形态结构、抑制粘釜现象等。用后过渡金属催化剂与其他过渡金属催化剂(如Ziegler-Natta催化剂、茂金属催化剂等)进行复合的目的主要是制备具有某些特定性能聚烯烃产物及使单一乙烯单体聚合制备支化聚乙烯。后过渡金属催化剂进行负载和复合后在改善聚烯烃产物性能、降低生产成本等方面有突出的优势．具有十分广阔的工业应用前景。     

无机离子交换剂的Na-NH4^＋离子交换特性

研究以天然沸石为基体制备无机离子交换剂的方法;利用离子交换剂的吸附等温曲线,可得到阳离子最大的交换容量;通过离子交换剂的吸附动力学曲线,可求得吸附平衡时间。结果表明,以改性剂M为改性材料,在天然沸石与改性剂M质量比为4：1时制得的无机离子交换剂的阳离子交换容量最高,常温时能达50mg／g,平衡吸附时间约为2h。     

Preliminary evaluation of polymeric Fe‐ and Al‐modified clays as adsorbents for heavy metal removal in water treatment

This paper assesses the potential of modified montmorillonite clays as low‐cost adsorbents/ion‐exchangers for the removal of trace level heavy metals (Cd, Cu, Ni, Pb and Zn) from potable water. Modification of the montmorillonites resulted in the exchange of the interlayer calcium ions for the polymeric species. One unmodified montmorillonite and three polymeric Fe‐ and Al‐modified montmorillonites have been evaluated with respect to their selectivity and uptake performance. All of the clays are selective for Pb and Cu adsorption from aqueous solutions at the mildly acidic pH range in which the experiments were performed (pH 5.5–6). Polymeric iron‐ and polymeric Al/Fe‐modified clays had comparatively great affinities for all the metals studied, whilst the original and polymeric Al modified clays had relatively lower affinities. Only the uptake of Pb and Cu could be correlated with physical properties such as clay surface area. The metal selectivity could be correlated to the type of intercalated polymeric Fe and Al species of the modified clays. © 2002 Society of Chemical Industry     

合成对叔辛基酚的试探性研究

对叔辛基酚（ＰＴＯＰ）作为二异丁烯（ＤＩＢ）的下游产品,是一种用途广泛、具有广阔的市场前景的精细化工产品。通过优化工艺条件,利用国产阳离子交换树脂Ｃ１０２－２／９８２６,在苯酚（ＰｈＯＨ）与ＤＩＢ摩尔比为３：１,催化剂加入量０．４２％（重量比）,反应温度８０℃条件下,接触２小时ＤＩＢ转化率达到９８．７９％以上,产物中ＰＴＯＰ选择性可达８９．３９％,蒸馏后产品纯度大于９８．００％。     

用于烷基化反应的离子液体催化剂研究进展

介绍了烷基化催化剂的特点及发展历程,概述了离子液体催化剂的分类和优点,讨论了离子液体催化烷基化的研究情况,包括异构烷烃与烯烃烷基化和芳香烃烷基化,最后,展望了离子液体催化剂在烷基化反应中的应用前景。     

Ion transport phenomena in polymeric electrolytes

The aim of the present work is to generalize an ion transport phenomena observed in composite polymeric electrolytes using the previously developed models as well as design a new approach which would be helpful in describing changes in conductivity and lithium ion transference numbers occurring upon addition of fillers to polymeric electrolytes. The concept is based on the observation of changes in ionic associations in the polymeric electrolytes studied in a wide salt concentration range. The idea is illustrated by the results coming from a variety of electrochemical and structural data obtained for composite electrolytes containing specially designed inorganic and organic fillers.     

烯烃环氧化钼系催化剂的多相化研究进展

介绍了以有机聚合物和无机硅酸盐为载体，负载钼催化剂及其对烯烃环氧化反应催化性能的研究进展；分析了硼酸树脂、乙烯-丙烯橡胶、螯合树脂、苯并吡咯树脂、聚酰亚胺树脂、聚硅氧烷树脂、阳离子交换树脂和聚苯乙烯等有机聚合物为载体的研究情况；评价了以无机硅酸盐为载体，采用溶胶-凝胶、离子交换、同晶取代等方法负载钼对催化性能的影响；展望了多相化烯烃环氧化钼系催化剂的发展前景。     

Removal of metals and anions from drinking water by ion exchange

Five organic and two inorganic ion exchangers were evaluated for the removal of metals and anions from water of two drilled wells. Sodium titanate (CoTreat) and a chelating aminophosphonate resin were the most efficient exchangers in removing transition metals from the total of 1800 bed volumes processed. CoTreat was the best for almost all of the transition metals. The breakthrough level of manganese was below 1% with CoTreat even when its concentration in the feed water was high (1 mg/l). The weak acid cation resin took up transition metals relatively efficiently. Somewhat unexpectedly, the cation exchangers also removed arsenic from water. Arsenic may have been sorbed on iron species, which again was adsorbed and filtered by the exchanger beds. Most of the cation exchangers took up calcium and magnesium at low processing capacities (<400 BV), and the strong base anion resin took up nitrate, bromide and sulphate very efficiently below 700 bed volumes. Neither chloride nor fluoride was taken up by the exchangers tested.