DIPHASIC ACIDO-BASIC PROPERTIES OF DI(OCTYLPHENYL)PHOSPHORIC ACID (DOPPA)

ABSTRACT

In the first part of this work, the diphasic acido-basic constant (pka*) of di(octylphenyl)phosphoric acid, denoted hereafter DOPPA or HL, is determined from its experimental diphasic neutralization curve. The pka* value of DOPPA appears to be equal to 2.6 in the presence of 1 mol/dm³ sodium salt. Such a value is significantly lower than that previously determined for di(2-ethylhexyl) phosphoric acid (DEHPA, pka* = 5.2), 2-ethylhexylphosphonic acid, mono-2-ethylhexyl ester (PC88A®, pka* = 7.1) and di(2,4,4-trimethylpentyl)phosphinic acid (CYANEX® 272, pka* = 8.7). DOPPA (HL) is definitely more acidic than the other organophosphorus acids because its acidic proton can be easily exchanged with sodium cation to form Na⁺;HL₂- species in organic phase. In the second and final part of the work, molecular modelling is used to model the dimers of various organophosphorus acids. A structure-activity relationship is obtained between the association energies of modelled dimers and their diphasic acido-basic constants. This relationship is then used for predicting the pka* values of DOPPOA and DOPPIA which are the phosphonic and phosphinic analogs of DOPPA, respectively.     

High speed direct injection (DI) light-fuel (gasoline) fumigated vehicle diesel engine

In the presented study, the effects of light-fuel fumigation on diesel engine cycle and characteristics have been examined theoretically. For this purpose, a computer program has been developed for prediction diesel engine cycles and engine characteristics in the cases of neat diesel fuel (NDF) and light-fuel (LF) fumigation. Here, gasoline is used as fumigated (supplementary) light fuel. For calculation of diesel engine cycle, quasi-dimensional phenomenological combustion model developed by Shahed and then Ottikkutti has been used and developed with new assumptions. Firstly, it has been proved that the developed engine cycle model for NDF and LF fumigation gives correct results by comparing with relevant experimental and theoretical studies. Then, for selected 2-10% gasoline ratios LF fumigation is investigated at varied equivalence ratio (VER) and constant equivalence ratios (CER). As a result, it has been determined that increasing gasoline fumigation at VER effective power and carbon monoxide (CO) ratio increase however, nitric oxide (NO) concentration decreases. Also, effective efficiency and specific fuel consumption (SFC) remain nearly constant in this case. Effective power, effective efficiency and CO ratio increase generally by increasing the gasoline fumigation ratio but SFC and NO concentration decrease generally at CER. Furthermore, this case is economic at high engine speeds.     

磷酸二(2,3-二氯丙基)-2-乙基己酯的合成

研究了一种新型增塑阻燃剂——磷酸二(2,3-二氯丙基)-2-乙基己酯的合成方法,并对催化剂的用量与反应温度的关系及反应时间与产率的关系等进行了研究。实验结果产品总得率可达95％。     

二(2-乙基己基)磷酸萃取L-苯丙氨酸

以二（2-乙基己基）磷酸（D2EHPA）-正辛烷萃取L-苯丙氨酸为对象,研究了D2EHPA浓度、L-苯丙氨酸初始浓度以及pH值对萃取平衡分配系数的影响。不同pH值下负载有机相的红外谱图分析表明,D2EHPA与L-苯丙氨酸形成的萃合物结构与pH值无关。提出了在萃取过程中同时存在着离子交换反应和质子转移反应的观点。1个氨基酸分子与2个二（2-乙基己基）磷酸二聚体相结合。本文建立的萃取平衡分配系数关联式,拟合精度令人满意。     

二(2-乙基己基)磷酸萃取L-色氨酸

以二 (2 -乙基己基 )磷酸 (D2EHPA) -正辛烷 (体系A)及D2EHPA -正辛醇 +正辛烷 (体系B)萃取L -色氨酸为对象 ,研究了D2EHPA浓度、L -色氨酸初始浓度、稀释剂组成以及pH值对萃取平衡分配系数的影响 .结果表明 ,在实验研究涉及的pH值 (1.0     

LEAD(II) EXTRACTION FROM NITRATE SOLUTIONS WITH DI(2-ETHYLHEXYL)PHOSPHORIC ACID

ABSTRACT

In this paper, equilibrium studies were carried out on the extraction of trace amounts of lead(II) from 0.2 mol/dm³ (Na,H)NO₃ aqueous solutions with di(2-ethylhexy1)phosphoric acid (HR) dissolved in n-dodecane at 298 K. The composition of the extracted species was numerically found to be and ₂. A chemical equilibrium model was developed to evaluate the thermodynamic constants for the formation of the two complexes, based on the law of mass action, which took into account the activity corrections of reactive species in the aqueous phase by employing the Bromley and the simplified Pitzer equations and those of the extractant in the organic phase.     

二（β－丁氧甲酰乙基）锡二氯化物的合成新工艺

在水体系中用锡粉、丙烯酸丁酯等原料，直接合成二（β－丁氧甲酰乙基）锡二氯化物。对反应温度、溶剂、组分摩尔比、催化剂选择及催化剂用量进行了系统规律性试验。     

长链烷基叔胺中微量烷基伯胺的测定

本文对分光光度法测定长链烷基叔胺中微量长链烷基伯胺的方法进行了考察。用1-氟-2,4-二硝基苯使伯胺衍生化,用环已烷萃取衍生物进行分光光度测定,叔胺对此无干扰。     

N，N－双（1－羟基－戊醛基）－5，5－二甲基海因的合成研究

利用５，５－二甲基海因与戊二醛的缩合反应合成标题化合物（１），该化合物是一种新型高效消毒剂。对其杀菌消毒能力进行了初步测试。     

新型磷酸酯DCPDCCP和DDCPCCP的合成

合成了2，3-二氯丙基二（2-氯环己基）磷酸酯和二（2，3-二氯丙基）-2-氯环己基磷酸酯二种新型混合磷酸酯。用元素分析，FT-IR表征了这二种化合物的结构，测定了粘度、密度等物理性能。探讨了反应条件对收率的影响。     

受阻胺类光稳定剂

以目前广泛使用的受阻胺类光稳定剂 (HALS)为出发点 ,论述了此类光稳定剂的结构、品种、光稳定机理、使用要求、发展趋势等。重点讨论了HALS与其他助剂的并用效果和HALS新产品开发状况。     

EXTRACTION CHEMISTRY OF COBALT AND NICKEL BY DI(1-METHYLHEPTYL)PHOSPHINIC ACID

The fundamental characteristics and mechanism of extraction of cobalt (II) and nickel(II) by di-(1-methylheptyl) phosphinic acid (DMHPA) were studied. The extraction ability of cobalt(II), nickel (II) and various metals by DMHPA decreases in the order Fe(III) > Zn ? Pb(II) > Mn(II) > Cu(II) > Co(II) > Mg > Ca > Ni(II). The difference of the pH_½ values for nickel and cobalt reaches 2.06 pH units, which is apparently greater than those from extraction by di(2-ethylhexyl)phosphoric acid (DEHPA)and 2-ethyl-hexyl ester 2-ethylhexylphosphonic acid(DHEHPA).The slope analysis and IR spectroscopy reveal that the stoichiometrics of cobalt and nickel extracted species are Co(HA₂)₂ and Ni(HA₂)₂(H₂O)₂ respectively. As demonstrated by the study of the electronic spectroscopy the structure of the extracted complexes were shown as tetrahedral and octahedral configuration respectively. Furthermore, the coordination field parameters of the complexes were calculated.     

SOLVENT EXTRACTION OF PALLADIUM FROM CHLORIDE SOLUTIONS BY ALKYLAMMONIUM DI(2-ETHYLHEXYL)DITHIOPHOSPHATES

ABSTRACT

The extraction of palladium (II) from chloride solutions (over a wide region of aqueous acidity) by di(2-ethylhexyl)dithiophosphates of tetraoctylammonium, tri-n-octylammonium and di-n-octylammonium in toluene at the constant chloride concentration has been studied. A synergistic effect was shown to be observed in these systems and it is explained by the formation of unusual complexes with mixed ligands. It has been established the palladium complexes, such as (R₃NH)[PdCl₂A], (R₃NH)[PdCl₂A] and (R₂NH₂)[PdCl₂A], involving both alkylammonium cation and dialkyldithiophosphate anion are extracted under conditions of the loaded organic phase using distribution methods depending on a composition of aqueous and organic phase. At the excess of R₃NHA or R₂NH·HA, PdA₂ is extracted into the organic phase. Table 8 reports the results obtained and indicates the domains of existence of the various species of palladium (II) extracted into the organic phase in the binary ex-tractant systems in comparison with the initial systems     

某些高分子受阻胺对聚丙烯稳定化作用的研究

众所周知,受阻胺光稳定剂对聚烯烃有良好的光稳定效率,已引起世界的注意。然而,小分子量的受阻胺易于挥发,从而影响它的效率发挥,为了克服这个缺点,使小分子受阻胺的高分子化是近年来受阻胺光稳定剂发展的方向,本文主要是研究三种商品化高分子受阻胺光稳定剂对聚丙烯的稳定化作用及其效率和机理。     

SYNERGISTIC EXTRACTION OF ZINC(II) BY MIXTURES OF PRIMARY AMINE N1923 AND CYANEX272

ABSTRACT

The extraction of zinc(II) and cadmium(II) from chloride solution by mixtures of primary amine N1923 and Cyanex272 (HA) was studied. The synergistic effect was observed for the extraction of zinc(II) while no synergistic effect for cadmium(II), which makes it possible to separate zinc(II) and cadmium(II) with the mixtures. The results showed that zinc(II) was extracted as (RNH₃Cl)₃·ZnClA instead of ZnA₂·2HA which was extracted by Cyanex272 alone. The extraction mechanism was discussed and the formation constants and thermodynamic functions were determined. The separation factors between zinc(II) and cadmium(II) were calculated.     

EXTRACTION AND SEPARATION OF HEAVY RARE EARTH(III) WITH EXTRACTION RESIN CONTAINING DI(2,4,4-TRIMETHYL PENTYL) PHOSPHINIC ACID (CYANEX 272)

ABSTRACT

Extraction resins, of the type of Levextrel, (which is a collective term for styrene/divinylbenzene based copolymers of predominantly macroporous structure that contain a selective extractant) are important for the recovery and separation of metal ions, as they combine features of solvent extraction and ion exchange resins. This paper presents the results of the adsorption of heavy rare earth ions (Ho(III), Er(III), Tm(III), Yb(III), Lu(III) and Y(II1)) from hydrochloric acid solutions at 0.2 mol/L ionic strength and 50°C by the extraction resin containing di (2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272) and the chromatographic separation of (Er(III), Tm(III) and Yb(III)). Technological separation products, with purity and yield of Tm₂O3 >99.97%, >80%; Er₂O₃ >99.9%, >94% and Yb₂O₃ >99.8%, >80% respectively, have been obtained from a feed having the composition Tm₂O₃ 60%, Er₂O₃ 10%, and Yb₂O₃ 3%, the others 27%.

The distribution coefficients, extraction equilibrium constants and separation factors have been determined as a function of acidity, loading of the resin and rare earths, flow rates and column ratios. The resolutions and efficiencies of separation of Er/Tm/Yb each other have been calculated. The stoichiometry of the extraction of rare earth ions has been suggested as well.     

聚酰胺树脂中胺值的测定

本文主要介绍用高氯酸一冰醋酸非水滴定法测定聚酰胺树脂中的胺值。该法简便、快速、灵敏且结果准确,可以作为聚酰胺树脂合成中控制其产品质量的主要质量中控方法。     

一步法合成抗氧剂1010

在容积为１５Ｌ的不锈钢间歇反应器中进行了“一步法”合成抗氧剂１０１０的实验研究，采取了适合于工业生产的催化剂制造方法，确定了较佳的工艺条件，给出了稳定运行实验结果，产品收率远高于国内传统工艺，产品质量达到国际同类产品先进指标。     

双功能受阻胺光稳定剂GW-540与紫外线吸收剂并用效应的研究

本文用IR、UV、SEM等方法,研究了双功能基受阻胺光稳定剂——三(1,2,2,6,6-五甲基-4-哌啶基)亚磷酸酯(GW-540),与紫外线吸收剂UV-531、UV-327并用时对聚丙烯的防光作用,结果表明:GW-540-UV-531并用体系有良好的防光作用,呈强的协同效应;GW-540-UV-327并用体系呈弱的对抗作用。结果还表明:GW-540对531和327的光分解均有保护作用.电镜研究表明,加入GW-540后,使UV-327在聚丙烯中分散更不均匀,从而影响其效率的发挥。文中提出了两个体系的协同和对抗作用机理。     

N-烯丙基芳胺改性双马来酰亚胺的研究

文中详细介绍了以N-烯丙基芳胺改性BMI所得树脂体系的工艺性和固化物的力学性能、耐热性和耐湿热性。