邻苯二甲酸二辛酯的催化研究进展

综述了国内外有关邻苯二甲酸二辛酯反应各种催化剂的催化性能及研究动态与进展,并对其发展前景做了预测。     

邻苯二甲酸二异辛酯在铜绿假单胞菌作用下的共代谢降解

选用铜绿假单胞菌为降解菌,研究了苯酚、葡萄糖、乙酸钠参与下,邻苯二甲酸二异辛酯(DEHP)的共代谢降解,挑选出了最佳的共代谢基质乙酸钠,并得到了最佳共代谢降解条件:p H=7、T=30℃、转速=200 rpm、共代谢基质与DEHP的浓度比=10∶1。最后对共代谢基质参与下的DEHP的降解过程进行了一级动力学拟合,拟合结果表明速率常数K苯酚K葡萄糖K乙酸钠。     

二(2-乙基己基)磷酸钠离子交换萃取氨基葡萄糖盐酸盐的研究

氨基葡萄糖盐酸盐极性大,传统物理萃取方法分离效果不理想,今采用离子交换萃取方法用二(2-乙基己基)磷酸钠萃取氨基葡萄糖盐酸盐溶液。测定了氨基葡萄糖盐酸盐初始浓度、萃取温度、萃取剂初始浓度、以及pH值对分配系数的影响。结果表明,在其他实验条件相同的情况下,分配系数随温度变化不明显,随二(2-乙基己基)磷酸钠初始浓度增加而增大,随氨基葡萄糖盐酸盐初始浓度增加而减少,随pH值增加先增大后减小;氨基葡萄糖盐酸盐低浓度下的分配系数远大于其高浓度下的分配系数;为获得最佳萃取效果,萃取平衡体系要尽量接近中性。建立了分配系数模型,并讨论了四种特殊情况下的分配系数表达式。研究结果为工业用离子交换萃取法分离氨基葡萄糖盐酸盐提供了一定的技术依据。     

可见光催化降解水中邻苯二甲酸二异辛酯的研究

邻苯二甲酸二异辛酯(DEHP)是环境激素类物质的一种,在环境中该物质持久存在不易分解,对人体健康造成严重危害,因此研究其废水降解具有重要的意义。以氙灯作为可见光光源,纳米CuPcTs/TiO2为催化剂,在可见光照射下较系统地考察了催化剂的活性、初始溶液的pH值、催化剂用量、光照时间等因素,对水溶液中DEHP光催化降解进行了研究。结果表明在pH=5,催化剂用量为0.4 g/L,光照时间为50 min,初始浓度为10 mg/L的DEHP水溶液降解速率为最佳,降解率达到93.6%,并证明了只有在催化剂和光源协同作用时,水中DEHP才可获得较快的降解。     

用废涤纶丝合成对苯二甲酸二（2－乙基己）酯及应用

本文介绍了以废涤纶丝为主要原料，用酯交换法生产对苯二甲酸二（２－乙基已）酯（ＤＯＴＰ），使用了一种新催化剂，大大缩短反应时间，并介绍了ＤＯＴＰ的应用情况。     

Solvent extraction kinetics of Sm(Ⅲ),Eu(Ⅲ) and Gd(Ⅲ) with 2-ethylhexyl phosphoric acid-2-ethylhexyl ester

Solvent extraction kinetics of Sm(Ⅲ), Eu(Ⅲ) and Gd(Ⅲ) from hydrochloric acid have been focused on using2-ethylhexyl phosphoric acid-2-ethylhexyl ester(P507) with Anordning for Kontinuerlig Undersokning av Fordelningsfaktore vid Vatske Extraction(AKUFVE). Compared with the conventional set-up, some advantages emerge obviously, for example, fast phase separation, easy operation and convenience of kinetic data acquisition.First of all, the extraction mechanism was discussed based on the dimeric model of P507. Secondly, the effects of stirring speed were investigated and 420 r·min~(-1) was determined of the following experiments. The effects of pH, concentration of rare earth elements(REEs) and P507 on the extraction rate were analyzed. The results indicated that the extraction mechanism changed with the increasing concentration of P507. Then, the experiments with different temperature were carried out. It turned out that the values of apparent activation energy(E_a) for Sm(Ⅲ), Eu(Ⅲ) and Gd(Ⅲ) extracted by P507 were 26.80 kJ·mol~(-1), 13.40 kJ·mol~(-1) and11.10 kJ·mol~(-1) respectively, the resistance of the entire process was limited by diffusion or both of diffusion and reaction. Finally, the correlation equations were obtained, and the theoretical results fit with the experimental data well, most relative error was within ±30%.     

邻苯二甲酸二乙基己酯对金鲫鱼脑组织和肾脏的氧化损伤作用

研究了邻苯二甲酸二乙基己酯(DEHP)对金鲫鱼脑组织和肾脏的氧化损伤程度及其发生机制.结果表明,DEHP会造成金鲫鱼脑组织和肾脏的氧化损伤,随着DEHP浓度的升高,超氧化物歧化酶活力先升高后降低,丙二醛含量不断上升,呈明显的剂量一效应关系.     

活性炭与光催化联用降解水中邻苯二甲酸二(2-乙基己)酯的研究

研究了臭氧活性炭与光催化联用降解饮用水中邻苯二甲酸二(2-乙基己)酯(DEHP)。当使用臭氧浓度为2.0mg/L、活性炭负载TiO_2催化剂浓度为0.02g/g、pH值10.0时,对DEHP含量为12.04mg/L的饮用水光催化降解6h,DEHP的去除率可达99.5%。研究结果表明,臭氧活性炭与光催化联用可有效去除水中邻苯二甲酸二(2-乙基己)酯。     

端羟基聚丙烯酸异辛酯及聚丙烯酸异辛酯-氨酯的制备及表征

采用原子转移自由基聚合(ATRP)合成了分子量与设计分子量(2000)大小相符的聚丙烯酸异辛酯,再以N-甲基单乙醇胺作为亲核试剂,对活性端基溴进行亲核取代,得到了分子量可控、分子量分布较窄的线型端羟基聚丙烯酸异辛酯。以此为原料与甲苯二异氰酸酯(TDI)反应,制备得到了聚丙烯酸异辛酯-氨酯。利用核磁共振谱(1HNMR)、差示扫描量热仪(DSC)、热重示差扫描量热仪(TGA)对合成的端羟基聚丙烯酸异辛酯及聚丙烯酸酯异辛酯-氨酯的结构、热稳定性等进行了表征。结果表明,利用端羟基聚丙烯酸异辛酯成功地制备了聚丙烯酸异辛酯-氨酯,由凝胶渗透色谱仪(GPC)测得其分子量为10200,玻璃化转变温度为-54℃,是一种新型的丙烯酸酯与聚氨酯的共聚物。     

Dilute solution properties of poly(2-methoxycyanurate) of bisphenol F and bisphenol A

Poly(2-methoxycyanurate) of bisphenol F and bisphenol A (PMCBFA) was synthesized and fractionated by a fractional precipitation method. The fractions were characterized by viscometry, osmometry and gel permeation chromatography. The Mark–Houwink–Kuhn–Sakurada (MHKS) parameters were established in four solvents and at four different temperatures. The unperturbed dimensions and their coefficients in different solvents were computed using the Stockmayer–Fixman excluded volume theory. From the solution study it was found that PMCBFA is highly flexible. This may be due to the ether linkage present in the main chain.     

Identification of 2-ethylhexyl hydrogen sebacate in bis(2-ethylhexyl) sebacate synthetic oils

Summary The acid monoester 2-ethylhexyl hydrogen sebacate has been identified in bis(2-ethylhexyl) sebacate oils by carrying out a partial separation of components with the solvents Skellysolve C and acetonitrile-methanol and by examining the infrared spectrum of the fraction contained in the acetonitrile-methanol phase for the characteristic 1,710- and 1,740-cm.⁻¹ absorption peaks of the monoester.     

Alteration of hepatic phospholipids in rats and mice by feeding di-(2-ethylhexyl)adipate and di-(2-ethylhexyl)phthalate

Effects of di-(2-ethylhexyl)adipate (DOA) and di-(2-ethylhexyl)phthalate (DEHP), plasticizers for polyvinylchloride products, on concentrations and compositions of hepatic phospholipids were studied in rats. When administered to rats at a 2% level for 2 wk, both DOA and DEHP caused a hepatomegaly, an increase in hepatic phospholipids and a decrease in the ratio of phosphatidylcholine (PC) to phosphatidylethanolamine (PE). In the comparable study with mice, the alkyl moiety of DOA was found to be responsible for these alterations. DOA and DEHP specifically altered fatty acid compositions of PC and PE: there was an increase in oleic and palmitic acids and a decrease in stearic and docosahexaenoic acids in PC and an increase in arachidonic acid at the expense of docosahexaenoic acid in PE. In addition, DOA caused an increase in the trienoic and tetraenoic molecular species in PC and an increase in the 1-palmitoyl-2-arachidonyl (16∶0//20∶4) species in PE. Thus, the effects of DOA on the lipid dynamics resembled those observed with DEHP, although the magnitude was slightly moderated.     

Recovery and Separation of Lanthanum(III), Aluminum(III), Cobalt(II), and Nickel(II) from Misch Metal by Solvent Extraction Using Bis(2-ethylhexyl) phosphinic Acid

Abstract

This paper describes use of bis(2-ethylhexyl) phosphinic acid as a reagent for extraction and mutual separation of lanthanum(III), aluminum(II), cobalt(II), and nickel(II) in 1.0 mol/L sodium nitrate. The extraction and stripping behavior of the four metal ions has been investigated using the extractant in Solvesso #150 as a diluent. The mutual separation and recovery of the metal ions from their mixtures has been tested by multistage extraction with a conventional separator funnel. A set of separation schemes has also been proposed for a continuous countercurrent multistage extraction which is comprised of ten extraction stages, four scrubbing stages, and seven stripping stages. Lanthanum(III) and aluminum(III) are coextracted but separated by selective stripping into different concentrations of hydrochloric acid. Cobalt(II) can be extracted with the nickel(II)-preloaded extractant solution, whereas nickel(II) remains in the aqueous phase. The successful separation of these metal ions from a misch metal-simulated sample is presented.     

Liquid-Liquid Extraction of Vanadium(V) and Niobium(V) with Tris(2-ethylhexyl)phosphate: Mutual Separation of Vanadium(V), Niobium(V), and Tantalum(V), and Analysis of Steel Samples

Abstract

Tris(2-ethylhexyl)phosphate (TEHP) dissolved in toluene is used for selective extraction of vanadium(V) and niobium(V) from hydrochloric and hydrobromic acid solution. Vanadium is determined spectrophotometrically after backextraction from TEHP, whereas unstripped niobium is determined in the TEHP phase with thiocyanate. The probable extractable species is VOCl₃·2TEHP or NbOCl₃·2TEHP/NbOBr₃·2TEHP. The method permits mutual separation of vanadium(V), niobium(V), and tantalum(V), and provides analysis of vanadium and niobium in alloys with a high degree of accuracy and precision.     

二（2—乙基己基）硫代磷酸的合成

研究了新型萃取剂二(2-乙基己基)硫代磷酸的合成、纯化及结构鉴定。     

琥珀酸二异辛酯磺酸钠的制备

介绍了一种在常压、无外加相转移催化剂的条件下制备琥珀酸二异辛酯磺酸钠的新方法。研究了合成标题产物中磺化反应的主要影响因素 ,并得出该反应的优惠工艺条件     

Effect of Bis-(2-ethylhexyl)Phosphoric Acid on Sodium Bis-(2-ethylhexyl)Phosphate Microemulsion for Selective Extraction of Non-Ferrous Metals

The effect of bis-(2-ethylhexyl)phosphoric acid (DEHPA) on the region of existence, conductivity and structure of sodium bis-(2-ethylhexyl)phosphate (NaDEHP) microemulsion has a dual nature and depends on DEHPA concentration. In the system NaDEHP–DEHPA–kerosene–water, the narrowing of the microemulsion region is observed with DEHPA concentration in the organic phase growth from 0.1 to 0.5 mol/L. The increase of DEHPA concentration in the organic phase from 0.1 to 0.4 mol/L leads to the reduction of electrical conductivity of the microemulsions. Based on the conductivity and viscosity measurements, we suppose the transition from reverse microemulsion with isolated droplets to percolate microemulsion at volume fraction of water 0.18 ( \(W = C_{{H_{2} O}} /C_{\text{NaDEHP}}\)  = 8). Droplet size of the microemulsions increases linearly with W growth. The rise of DEHPA concentration in the organic phase from 0.1 to 0.3 mol/L causes the growth of the coefficient at W in the equation d = kW + b from 0.038 to 0.249, i.e., it increases the slope of the lines. In contrast, DEHPA introduction at the concentration 0.1 mol/L (in the organic phase) leads to the expansion of the microemulsion region, does not affect the conductivity and decreases the coefficient at W. The rate of copper recovery into the microemulsion increases considerably with the rise of DEHPA concentration from 0.0 to 0.3 mol/L; no dual effect is observed. The following composition of the microemulsion for non-ferrous metals leaching is recommended: C _NaDEHP = 1.6 mol/L, C _DEHPA = 0.3 mol/L (in the organic phase); W = 8–32.     

无毒增塑剂柠檬酸三(2-乙基)己酯的合成

以柠檬酸和2-乙基己醇为原料,用氧化二正丁基锡为催化剂合成了无毒增塑剂柠檬酸三(2-乙基)己酯,考察了反应温度、催化剂用量、醇酸摩尔比、反应时间等因素对反应结果的影响,对合成的产品进行了红外光谱分析。实验结果表明,氧化二正丁基锡催化合成柠檬酸三(2-乙基)己酯的最佳反应条件为n(柠檬酸)∶n(2-乙基己醇)=1∶3.60,催化剂用量为柠檬酸质量的0.5%,反应时间为120min,反应温度为150～160℃,在最佳反应条件下,柠檬酸三(2-乙基)己酯收率在98%以上。