系列长链烷基萘磺酸钠的反相离子对高效液相色谱法的研究

对一系列长链烷基萘磺酸钠，包括己基萘磺酸钠、辛基萘磺酸钠、癸基萘磺酸钠、十二烷基萘磺酸钠、双己基萘磺酸钠和双辛基萘磺酸钠，通过电喷雾质谱及反相离子对高效液相色谱对这些化合物进行了表征。并得到了最佳液相色谱分离条件。在最佳分离条件下，利用这些数据分析了3种混合烷基萘磺酸盐工业品中的主要成分。     

羟甲基化木质素磺酸盐添加剂对钻井液性能的影响

为了进一步优化木质素磺酸盐作为钻井液处理剂的效能,利用其与甲醛的羟甲基化反应制备了羟甲基化木质素磺酸盐;采用红外光谱仪、X射线粉末衍射仪、扫描电镜等分析了其结构;测定了改性前后的木质素磺酸盐对钻井液流变性、降滤失性、黏土水化膨胀抑制性等性能的影响.结果显示,改性后的羟甲基化木质素磺酸盐的整体结构变化不大,但羟基数量增加,与水的相溶性增强.与木质素磺酸盐相比,羟甲基化木质素磺酸盐在室温下对基浆有较强的提黏作用,经180℃高温老化后降黏、降滤失作用有所增强,形成的泥饼厚度降低,对黏土水化膨胀的抑制作用增强.     

三取代直链烷基苯磺酸钠的界面扩张性质

利用悬挂滴方法研究了五种表面活性剂3,4-二己基苯磺酸钠(66)、3,4-二庚基苯磺酸钠(77)、2-乙基-4,5-二己基苯磺酸钠(266)、2-丙基-4,5-二己基苯磺酸钠(366)和2-丁基-4,5-二己基苯磺酸钠(466)在空气-水和癸烷-水界面上的扩张流变性质,考察了烷基取代在苯环不同位置对分子界面行为的影响.研究发现,苯环不同位置的取代烷基链长变化对扩张弹性模量和扩张粘性模量影响不同.随着烷基链长增长,表面扩张弹性模量均增加,而扩张粘性模量表现则不同:邻位短链烷基碳数从2变化到4,对粘性模量贡献不大;而间位长链烷基增长对表面弛豫过程影响较大,粘性模量明显增大.油分子的插入能大大削弱间位长链烷基间的强相互作用,一方面导致界面弹性模量和粘性模量远低于表面,同时使得同分异构分子77和266的界面扩张粘性模量数值接近.     

Exploring Alkylated Ferrocene Sulfonates as Electrocatalysts for Sulfide Detection

Alkylated ferrocene sulfonate compounds, 1,1′‐dimethyl ferrocene sulfonate, t‐butyl ferrocene sulfonate, ethyl ferrocene sulfonate, and n‐butyl ferrocene sulfonate are explored for the electrocatalytic detection of sulfide at a boron‐doped diamond electrode. Voltammetric interrogation of the ferrocene sulfonate compounds is investigated to determine oxidizing potentials, diffusion coefficients and responses towards sulfide. In the latter case, measurement of the electrocatalytic rate constants by means of chronoamperometry indicates a high electrocatalytic activity (ca. 10³ M^?1 s^?1) towards sulfide.     

一种含磺酸酯基亲和性变化树脂的合成及其热分解性能研究

本实验合成了一系列含p-苯磺酸异丙酯基亲和性变化的二元、三元共聚物,并对其结构、聚合特征f1-F1曲线以及热分解性能进行了研究.对共聚物的DSC测试发现,随着p-苯磺酸异丙酯基含量的增加,树脂中磺酸酯基的分解温度向低温方向移动,范围在120-170℃;而磺酸酯基的分解能量随其在树脂中含量的增加而升高,范围在20-30kJ/mol.动力学研究结果显示,聚合物中磺酸酯基的热分解过程属于自加速类型,反映了热分解产生的磺酸对磺酸异丙酯热分解过程的催化作用.加热分解后树脂水溶性的研究表明,在二元共聚物中磺酸酯基单元含量等于或大于27%,在引入羧酸基的三元共聚物中磺酸酯基单元含量为21%时,热分解后共聚物涂层表现出优良的水溶性,能够在中性水中快速、彻底溶解并脱离支持版基.     

The dispersion of pigment slurries via incorporation with water-soluble sulfonate poly(ethylene terephthalate)

A water-soluble sulfonate poly(ethylene terephthalate) copolymer has been synthesized and identified as a high-temperature endurable surfactant. The glass-transition temperature and the storage modulus increase in correlation to the increase in sulfonate content. Various characterization studies were performed, including light scattering, zeta-potential measurement and a sedimentation test. The results suggest that at equal numbers of sulfonate units in a solution, a low concentration of a dispersant of high sulfonate content is more effective than a high concentration of a dispersant of low sulfonate content. Received: 6 April 2000 Accepted: 23 September 2000     

Emulsifier-free emulsion copolymerization of styrene and sodium styrene sulfonate

The kinetics of the emulsifier-free emulsion copolymerization of styrene and sodium styrene sulfonate have been examined over a range of comonomer compositions. The rate of polymerization was found to increase dramatically in the presence of small amounts of sodium styrene sulfonate. This increase is attributed to the increased number of particles formed when sodium styrene sulfonate was present and to a gel effect enhanced by ion association. At low concentrations of functional comonomer, where a monodisperse product was obtained, a homogeneous nucleation mechanism of particle generation is proposed. At higher concentrations, broader and then bimodal size distributions were obtained, and this is ascribed to significant aqueous phase polymerization of sodium styrene sulfonate. The water-soluble homopolymer is supposed to act as a locus of polymerization. The occurrence of this aqueous phase side reaction and the generation of secondary particles makes impossible the preparation of highly sulfonated polystyrene latexes by batch or seeded batch emulsion copolymerization.     

Studies of Synergism/Antagonism in Sodium Alkyl Benzene Sulfonate/Methyl Oleate Model Oil Systems

Experimental studies are conducted in order to elucidate the mechanisms responsible for synergism/antagonism for lowering interfacial tension in alkyl benzene sulfonate/brine/methyl oleate model oil and alkyl benzene sulfonate/alkali/methyl oleate model oil systems. We found that different mechanisms exist in above two systems. In alkyl benzene sulfonate/brine/methyl oleate model oil systems, methyl oleate influences the partition of added surfactants between oil and aqueous phase by changing equivalent alkane carbon number (EACN) value of model oil. In alkyl benzene sulfonate/alkali/methyl oleate model oil systems, methyl oleate in oil phase has two functions: on the one hand, it influences the partition of surfactant between oil and aqueous phase; on the other hand, it directly affects IFT by displacing surfactant molecule or forming mixed film with surfactant molecule at the interface.     

An analysis of the kinetics of oxidation of ascorbate at poly(aniline)-poly(styrene sulfonate) modified microelectrodes

A detailed kinetic study is provided for the oxidation of ascorbate at poly(aniline)-poly(styrene sulfonate) coated microelectrodes. Flat films with a low degree of polymer spillover and a thickness much lower than the microelectrode radius were produced by controlled potentiodynamic electrodeposition. The currents for ascorbate oxidation are found to be independent of the polymer thickness, indicating that the reaction occurs at the outer surface of the polymer film. At low ascorbate concentrations, below around 40 mM, the currents are found to be mass transport limited. At higher ascorbate concentrations the currents became kinetically limited. The experimental data for measurements at a range of potentials are fitted to a consistent kinetic model and the results summarized in a case diagram. The results obtained for the poly(aniline)-(polystyrene sulfonate) coated microelectrode are compared to those for a poly(aniline)-poly(vinyl sulfonate) coated microelectrode and to the results of an earlier study of the reaction at poly(aniline)-poly(vinyl sulfonate) coated rotating disc electrodes. For poly(aniline)-poly(styrene sulfonate) the oxidation of ascorbate is found to proceed by one electron reaction whereas for poly(aniline)-poly(vinyl sulfonate) the reaction is found to be a two electron oxidation.     

Mixed micelles of sodium 4-decyl naphthalene sulfonate with Triton X-100 and sodium dodecyl sulfonate analyzed by 1H NMR

The characteristics of sodium 4-decyl naphthalene sulfonate (SDNS)/Triton X-100 (TX-100) and sodium dodecyl sulfonate (SDSN)/SDNS mixed micelles with different molar ratios were studied by 1D and 2D 1H NMR. In the mixed micelle of SDNS/TX-100 the phenoxy rings of the TX-100 are embedded in the near vicinity of the alkyl chains of SDNS and its polyoxyethylene segments, but the first oxyethylene group, to which the phenoxy ring is adjacent, are located near the naphthyl rings. In the mixed micelle of the SDNS/SDSN system the sulfonate groups of SDSN are embedded in the naphthyl rings of SDNS; i.e., they are located more internally in the mixed hydrophobic micellar core than those of SDNS. Moreover, the naphthyl rings of SDNS separating these sulfonate groups of SDSN may play an active role in weakening the electrostatic repulsion of the negatively charged sulfonate groups, which favors the mixed micelle aggregation.     

聚全氟乙丙膜电子束引发预辐射接枝AA和SSS制备阳离子交换膜的研究

利用电子束引发预辐射接枝技术,在聚全氟乙丙烯(FEP)薄膜上接枝丙烯酸(AA)和对苯乙烯磺酸钠(SSS),制备一种含羧酸基团和磺酸基团的阳离子交换膜,详细研究了反应温度、单体总浓度、pH值变化、辐照气氛及添加剂对接枝率的影响规律,明确了实验条件与接枝率的对应关系。FTIR测试证明了接枝产物是全氟乙丙烯和丙烯酸、对苯乙烯磺酸钠的接枝共聚物。     

Synthesis and characterisation of water soluble ferrocenes: Molecular tuning of redox potentials

A range of novel water-soluble alkylated ferrocene sulfonate compounds are reported. Mono- and di-sulfonation on a series of alkyl ferrocenes produced 1,1′-dimethyl ferrocene sulfonate, 1,1′-dimethyl ferrocene disulfonate, 1,1′-diethyl ferrocene sulfonate, 1,1′-diethyl ferrocene disulfonate, t-butyl ferrocene sulfonate, t-butyl ferrocene disulfonate, ethyl ferrocene sulfonate, ethyl ferrocene disulfonate, n-butyl ferrocene sulfonate and n-butyl ferrocene disulfonate. All compounds were characterized by NMR spectroscopy, UV/Vis spectroscopy and electrochemical analysis. ¹H and ¹³C NMR studies have revealed the formation of several isomers with sulfonation occurring on positions α and β to the alkyl substituent or on the unsubstituted cyclopentadienyl ring. Variation of the alkyl group allowed the isomeric pattern to be tuned such that the final products followed either electronic or steric control. Cyclic voltammetry of the resulting products showed that the redox potential of the iron centre can be easily manipulated by changing the substituents on the cyclopentadienyl rings. This result has significant implications in the future development of homogenous redox mediators for sensing applications.     

Adsorption mechanism of mixed cationic/anionic collectors in feldspar-quartz flotation system

The adsorption mechanism of mixed cationic alkyl diamine and anionic sulfonate/oleate collectors at acidic pH values was investigated on microcline and quartz minerals through Hallimond flotation, electrokinetic and diffuse reflectance FTIR studies. In the presence of anionic collectors, neither of the minerals responded to flotation but the diamine flotation of the minerals was observed to be pH and concentration dependent. The presence of sulfonate enhanced the diamine flotation of the minerals by its co-adsorption. The difference in surface charge between the minerals at pH 2 was found to be the basis for preferential feldspar flotation from quartz in mixed diamine/sulfonate collectors. The infrared spectra revealed no adsorption of sulfonate collector when used alone but displayed its co-adsorption as diamine-sulfonate complex when used with diamine. The presence of sulfonate increased the diamine adsorption due to a decrease in the electrostatic head-head repulsion between the adjacent surface ammonium ions and thereby increasing the lateral tail-tail hydrophobic bonds. The mole ratio of diamine/sulfonate was found to be an important factor in the orientation of alkyl chains and thus the flotation response of minerals. The increase in sulfonate concentration beyond diamine concentration leads to the formation of soluble 1:2 diamine-sulfonate complex or precipitate and the adsorption of these species decreased the flotation since the alkyl chains are in chaotical orientation with a conceivable number of head groups directing towards the solution phase.     

Simulation study of the equilibrium morphology in ionomers with different architectures

The influence of the side chain and the backbone segment length on the shape of the hydrophilic clusters in an ionomer with sulfonate‐terminated side chains is investigated by molecular dynamics computer simulations. Different ionomer architectures, ranging from Nafion‐like molecules to ionomer structures with extremely long side chains and backbone segments, are analyzed. It is shown that the size and the sulfonate population of hydrophilic clusters are differently affected by the variation of the backbone length in homologous membranes. Although the clusters swell when the backbone length is increased, they contain fewer head groups, and the average sulfonate–sulfonate separation in these swollen clusters becomes larger. An increase in the equivalent weight (EW) of homologous membranes thus hinders proton transport through hydrophilic channels. We also have shown that larger sulfonate clusters are formed in modified membranes with longer side chains. Compared to the case of membranes with shorter side chains but the same EW, those with longer side chains have a higher proton diffusivity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Rapid screening and quantification of sulfonate derivatives in white peony root by UHPLC–MS–MS

A rapid ultra-high-performance liquid chromatographic–tandem mass spectrometric (UHPLC–MS–MS) method has been developed for rapid screening and quantitative analysis of sulfonate derivatives (SDs) in commercial white peony root. Separation was performed on an Agilent Zorbax Eclipse Plus-C18 column by gradient elution with acetonitrile–0.1% (v/v) formic acid as the mobile phase. In-source fragmentation was used to generate the characteristic fragment ion at m/z 259 and to screen for nine SDs. Detection of these SDs was further performed in multiple reaction monitoring (MRM) mode to improve sensitivity and to quantify the two SDs paeoniflorin sulfonate and benzoylpaeoniflorin sulfonate. The method was validated for specificity, linearity, limits of detection and quantification, precision, accuracy, and matrix effects. Nine commercial white peony root samples were examined by use of this method, which revealed great variety in the paeoniflorin sulfonate and benzoylpaeoniflorin sulfonate content.     

Structural and electronic properties of PFOS and LiPFOS

The structural and electronic properties of perfluorinated surfactants perfluorooctane sulfonate (PFOS) and lithium perfluorooctane sulfonate (LiPFOS) have been investigated theoretically by performing semi-empirical molecular orbital theory at the level of AM1 calculations. The optimized structure and the electronic properties of the molecules are obtained.     

APPLICATION OF THE SULFONATE ESTER GROUP AS A LINKER FOR SOLID PHASE ORGANIC SYNTHESIS

A use of sulfonate ester as a linker in synthesis of w-aminoalkanols was reporte.Diols were tethered onto polystyryl sulfonyl chloride resin,yielding sulfonate resins(2).After cleaved by diethyl amine,diisopropylamine and propylamine respectively,three w-aminoalkanlos were obtained.     

Transport properties of Nafion membranes modified with tetrapropylammonium ions for direct methanol fuel cell application

This work presents a study of transport properties (proton conductivity, methanol permeability, and water uptake) and acid-base properties of commercial Nafion-112, -115, and -117 membranes modified with tetrapropylammonium (TPA) cations. In the interaction between TPA hydroxide and protons of sulfonate groups in the Nafion matrix, some of the protons are shown to be bound to sulfonate groups and do not participate in transport processes. These findings are confirmed by IR spectroscopy, acid-base titration, and data on proton conductivity of the modified membranes. Proton conductivity of the modified membranes is shown to be effectively described by a percolation model with parameters that agree with published data for commercial Nafion membranes. Based on these results, a model is proposed for the interaction of TPA cations with the sulfonate groups in Nafion membranes. According to this model, TPA cations form hydrophobic clusters in hydrophilic regions of the polymer matrix, thus preventing some of the protonated sulfonate groups from participating in transport processes.     

Synthesis of alpha-fluorosulfonate and alpha-fluorosulfonamide analogues of a sulfated carbohydrate

The first synthesis of sulfonamide and sulfonate analogues of a sulfated carbohydrate in which the ester oxygen of the sulfate is replaced with a CHF or CF2 group is reported. This was accomplished by electrophilic fluorination of the protected sulfonate and sulfonamide precursors. [reaction: see text].     

Syntheses and Crystal Structures of Potassium–Lanthanoid(III) Complexes with the 1,2‐Benzenedisulfonate Ligand

The complexes [K(H₂O)₂LnL₂] (Ln = La or Nd; L = 1,2‐benzenedisulfonate) and [K(H₂O)Yb(H₂O)₄L₂] were initially isolated fortuitously from attempts to prepare the corresponding Ln₂L₃ complexes from Ln₂O₃ and H₂L in water. Indeed the bulk products from these reactions have the composition Ln₂L₃. Subsequently, deliberate syntheses by reacting equimolar amounts of Ln₂L₃ with K₂L in water gave the complexes in good yield. X‐ray crystal structures of [K(H₂O)₂LnL₂] (Ln = La or Nd) showed the complexes to be isostructural with a two dimensional polymeric network structure in which LnL₂ units are linked into chains crosslinked by potassium ions. Each Ln is nine coordinate with solely sulfonate oxygen donor atoms. Between adjacent lanthanoid ions there are three different types of sulfonate bridges and two examples of each. Most noteworthy is highly unsymmetrical bridging through μ‐η²‐sulfonate oxygen atoms. Consequently, one Ln–O bond is ca. 0.5 Å longer than the other eight. Potassium is nine‐coordinate with seven sulfonate oxygen atoms and two aqua ligands, and surprisingly <K–O(sulfonate)> is much longer than <K–O(H₂O)>. Pairs of potassium ions are linked by two μ‐η²‐sulfonate oxygen atoms, which are unsymmetrically bridging. The structure of [K(H₂O)Yb(H₂O)₄L₂] comprises discrete tetranuclear units containing two independent ytterbium ions, each coordinated by four water molecules and two chelating (via seven membered rings) disulfonate ligands, and two potassium ions, each coordinated by six sulfonate oxygen atoms and a water molecule. For each potassium, four of the coordinated sulfonate oxygen atoms are from sulfonate ligands bonded to one ytterbium atom and two from sulfonate ligands attached to the other ytterbium atom. In contrast to the Nd and La complexes, <K–O(sulfonate)> is shorter than <K–O(H₂O)>.