Chemical Modification of Poly(Vinyl Chloride) with Ethylene Glycol and its Application in Ion-Chromatography

ABSTRACT

Poly(vinyl chloride) (PVC) has been chemically modified through crosslinking with different molar ratios of sodium ethylene glycoxide in ethylene glycol. The crosslinked PVC was used for coating of silica gel 60 particles and the obtained products were impregnated with tetramethylammonium hydroxide (TMAH). The crosslinking reaction as well as the insertion of TMAH were followed up and quantitatively determined with the aid of FT-IR spectroscopic and elemental analyses. The obtained materials were roughly tested for ion chromatographic separation of different ions. Retention time ( t _R) was determined for lithium, magnesium, strontium, and calcium cations whereas chloride, nitrate, and sulfate were selected as representatives for anions.     

Studies on extraction and permeation of lanthanum(III) and cerium(III) using cyphos IL 104 as extractant and ion carrier

ABSTRACT

This work shows application of Cyphos IL 104 (trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate) as the extractant and the ion carrier of Ce(III) and La(III) from aqueous solutions through polymer inclusion membranes (PIM). These membranes were used for separation of Ce(III) from solution containing La(III), Cu(II), Co(II) and Ni(II). The best results of the separation process were obtained for PIM containing: 20.0 wt.% CTA, 55.0 wt.% NPOE and 25.0 wt.% Cyphos IL 104 at pH 3.8 into 1 M H₂SO₄. The separation coefficients were found in order of S _Ce/La < S _Ce/Cu < S _Ce/Co < S _Ce/Ni.     

Synergistic Extraction of Some Rare Earths(III) from Nitrate Media by Thenoyltrifluoroacetone and Tri-n-octylamine

Abstract

The synergistic action of tri-n-octylamine (TOA) in the selective extraction of the rare earths La, Nd, Tm, Lu, and Y with thenoyltrifluoroacetone (HTTA) was studied in a nitrate media (0.6 M HNO₃ + 11.6 g/L CaO). The synergism enhances the REE extraction and separation. The [HTTA], [TOA], diluent, complexing agents, and calcium ion effects were also studied.     

Extraction Behavior of the Synergistic System 2,6‐ bis ‐(Benzoxazolyl)‐4‐ Dodecyloxylpyridine and 2‐Bromodecanoic Acid Using Am and Eu as Radioactive Tracers

Abstract

In this study, the extraction properties of a synergistic system consisting of 2,6‐bis‐(benzoxazolyl)‐4‐dodecyloxylpyridine (BODO) and 2‐bromodecanoic acid (HA) in tert‐butyl benzene (TBB) have been investigated as a function of ionic strength by varying the nitrate ion and perchlorate ion concentrations. The influence of the hydrogen ion concentration has also been investigated. Distribution ratios between 0.03–12 and 0.003–0.8 have been found for Am(III) and Eu(III), respectively, but there were no attempts to maximize these values. It has been shown that the distribution ratios decrease with increasing amounts of ClO₄ ^?, NO₃ ^?, and H⁺. The mechanisms, however, by which the decrease occurs, are different. In the case of increasing perchlorate ion concentration, the decrease in extraction is linear in a log–log plot of the distribution ratio vs. the ionic strength, while in the nitrate case the complexation between nitrate and Am or Eu increases at high nitrate ion concentrations and thereby decreases the distribution ratio in a non‐linear way. The decrease in extraction could be caused by changes in activity coefficients that can be explained with specific ion interaction theory (SIT); shielding of the metal ions, and by nitrate complexation with Am and Eu as competing mechanism at high ionic strengths. The separation factor between Am and Eu reaches a maximum at ～1 M nitrate ion concentration. Thereafter the values decrease with increasing nitrate ion concentrations.     

Thermal and NMR Studies of Polystyrene Blends

Abstract

The effect of addition of poly (propylene oxide) (PPO) and polystyrene with low molecular weight (LPS) to polystyrene (PS) was investigated blending these polymers in a Haake internal mixer. The PPO and LPS range was established up to 10% by weight. The blends were analysed by differential scanning calorimetry (DSC) and carbon-13 nuclear magnetic resonance spectroscopy at solid state (NMR), using conventional NMR techniques as cross-polarisation/magic angle spinning (CP/MAS) and proton spin-lattice relaxation time in the rotating frame (T ₁ ^H _p ). The addition of 1 and 5% of PPO and 5% of LPS to PS made the blends of PS/PPO and PS/LPS more rigid.     

Bis(Diphenylcarbamoylmethylphosphine Oxide) Ligand Containing 4, 7, 10 – Trioxatridecane Spacer: Novel Effective Extractant for Actinides and Lanthanides

A novel polydentate neutral organophosphorus ligand 1 containing two Ph₂P(O)CH₂C(O)NH- bidentate moieties connected by a 4, 7, 10 - trioxatridecane spacer through amide nitrogen atoms was synthesized and studied as an extractant for U(VI), Th(IV), and lanthanides(III) ions from HNO₃ solutions. The influence of aqueous and organic phases on the extraction efficiency was elucidated and stoichiometry of the complexes extracted was determined. Bis-CMPO ligand 1 was found to possess a higher extraction efficiency towards U(VI), Th(IV), and lanthanides(III) ions than its mono analog diphenylphosphorylacetic acid N-nonylamide 5 and bis-CMPO ligands containing a di- and a triethylene glycol spacers. The values of D_U, D_Th, and D_Ln for compound 1 are more than two orders of magnitude higher than those for its mono-CMPO analog 5.     

Programmed Multiple Development: The Solvent Advance and Removal Mechanisms,Isolated and Compared

Abstract

Throughout each programmed multiple development (PMD) in thin-layer chromatography (TLC), the thin-layer plate remains in contact with the solvent. An important result is a spot reconcentration that narrows spots of low as well as high R_F Spot reconcentration occurs as an interaction between the spot molecules and the solvent front, during both solvent advance and solvent removal. When solvent is removed by heating in PMD, two separate mechanisms for spot reconcentration exist: (a) solvent removal by heating, and (b) solvent advance that follows solvent removal by heating. These mechanisms have been experimentally isolated and studied quantitatively. A chromatographic quality index Q_MD = RR_W was used for expression of the results. Here R is resolution—the center-to-center separation of the spots divided by the average width of the spots—and R_w is the maximum ratio of the spot top-to-bottom widths in the chromatogram. To make the measurements of the developed spots more precise and clear, all spots were formed into rings before development. The measurements show that if solvent is removed conventionally—by air-drying the plate away from the solvent reservoir between developments—it matters little whether the successive solvent advances are uniform (Q_MD = 2.1) or successively more extended (Q_MD = 1.5). Both compare with straight PMD, for which Q_MD = 10.0. The chromatographic quality resulting from isolated solvent advances that follow solvent removal by heating is best for gentler, more prolonged heating (Q_MD = 3.0), but better for strong, brief heating (Q_MD = 2.3) than for no heating at all (Q^md = 1.5). The chromatographic quality resulting from solvent removal is better than that resulting from solvent advance whether the heating is as is preferable gentler and more prolonged (Q^mdremoval = 4.3, Q^md advance = 3.0), or strong and brief Q^md = 3.4), Q^md = 2.3). The full chromatographic quality of straight PMD (Q^md = 10.0) is obtained because the solvent advance and solvent removal mechanisms complement each other and are supplemented by prehead and initial, brief continuous development at the origin.     

Uranyl ion adsorptivity of N-vinyl 2-pyrrolidone/acrylonitrile copolymeric hydrogels containing amidoxime groups

Summary N-vinyl 2-pyrrolidone (VP) / Acrylonitrile (AN) copolymeric hydrogels were synthesized by using γ-radiation and amidoximated for the purpose of uranyl ion adsorption. Optimum amidoximation time was determined by following the uranyl ion, UO₂ ²⁺, adsorption capacity. The adsorption of amidoximated copolymers was studied from different uranyl ion solutions (1000–1850 ppm). The results of all adsorption studies showed that the interaction between UO₂ ²⁺ and amidoxime groups comply with Langmuir type isotherm. The adsorption capacity was found as 0.54 g UO₂ ²⁺ /g dry amidoximated copolymeric hydrogels. From the stoichiometric calculations, it was found that the bonding between UO₂ ²⁺ and amidoxime groups is 1 to 4. Received: 7 September 1999/Revised version: 21 February 2000/Accepted: 18 March 2000     

Lewis acid–base property of P(VDF‐co‐HFP) measured by inverse gas chromatography

Poly (vinylidene fluoride‐co‐hexafluoropropylene) P(VDF‐co‐HFP) is an excellent material for polymer electrolytes of lithium ion battery. To enhance the lithium ion transference number, some metal oxides were often embedded into P(VDF‐co‐HFP). The promising mechanism for the increase in lithium ionic conductivity was Lewis acid‐base theory. In this experiment, the Lewis acid–base properties of P(VDF‐co‐HFP) were measured by inverse gas chromatography (IGC). The Lewis acid constant K_a of P(VDF‐co‐HFP) is 0.254, and the base constant K_b is 1.199. Compared with other polymers characterized by IGC, P(VDF‐co‐HFP) is the strongest Lewis basic polymers. Except aluminum ion, lithium ion is the strongest Lewis acidic ion according to their η value of Lewis acids. Therefore, a strong Lewis acid–base interaction will exist between lithium ion and P(VDF‐co‐HFP). This will restrict the transference of lithium ion in P(VDF‐co‐HFP). To enhance the lithium ion transference by blending other metal ions into P(VDF‐co‐HFP), it is suggested that the preferential ions should be Al³⁺, Mg²⁺, Na⁺, and Ca²⁺ because these metal ions have relative large η values. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of functionlization of N,N-dibenzyldithiocarbamate: synthesis,spectral and structural studies on bis(N-benzyl-N-(4-methoxybenzyl)dithiocarbamato-S,S′)zinc(II) and bis(N-benzyl-N-(4-cholrobenzyl)dithiocarbamato-S,S′)cadmium(II) and their use for the preparation of MS (M = Zn,Cd)

Bis(N-benzyl-N-(4-methoxybenzyl)dithiocarbamato-S,S′)zinc(II) (1) and bis(N-benzyl-N-(4-chlorobenzyl)dithiocarbamato-S,S′)cadmium(II) (2) have been prepared and characterized by elemental analysis, IR and NMR (¹H and ¹³C) spectroscopy and single-crystal X-ray analysis. Complexes 1 and 2 exist as monomer and dimer, respectively. Crystal structures of 1 and 2 confirm the presence of four coordinated zinc in a distorted tetrahedral arrangement and five coordinated cadmium in a distorted square pyramid arrangement, respectively. Both the complexes are further stabilized by various interactions such as C–H···S, C–H···N, C–H···O and C–H···π (chelate). C–H···O interaction leads to the formation of dimer in complex 1. In complex 2, C–H···π (chelate) interaction runs in opposite directions which results in the polymeric chain. ZnS and CdS have been prepared from 1 and 2, respectively, and characterized by powder X-ray diffraction, SEM, UV–Vis and fluorescence spectroscopy. The X-ray diffraction pattern confirms the wurtzite phase of as-prepared ZnS and CdS.     

Indeno-Polycyclic Aromatic Hydrocarbons: A Versatile New Synthetic Route

Acylation of a polycyclic aromatic hydrocarbon (PAH) adjacent to a ring junction with 2-bromobenzoyl chloride followed by Flash Vacuum Pyrolysis (FVP) of the resulting bromoketone affords the corresponding indeno-annulated PAH. The new method is illustrated by syntheses of indeno[1,2,3-cd]pyrene (1) from pyrene and indeno[1,2,3-cd]fluoranthene (2) from fluoranthene. The formation of indeno[1,2,3,4-defg]chrysene (11) from FVP of 8-(2-bromobenzoyl)-fluoranthene (10), and as a secondary product from FVP of 3-(2-bromobenzoyl)fluoranthene (9), reveals the ability of phenyl groups to migrate around the periphery of a didehydro-PAH. Mechanisms involving reversible hydrogen atom transfers are proposed. Diacylation of fluoranthene with 2-bromobenzoyl chloride followed by FVP gives the previously unknown, nonplanar, nonalternant, C₂₈H₁₄ PAH diindeno[1,2,3,4-defg: 1,2,3-rs]chrysene (21) in just two steps.     

Sorption of Rare-earth Elements and Ac on DN resin with HCl,HClO4, CH3COOH,CCl3COOH

ABSTRACT

The distribution of some rare-earth elements (REE) on DN resin (TODGA loaded resin by Triskem international) was determined from different concentrations of two inorganic (HCl, HClO₄) and two organic acids (CH₃COOH, CCl₃COOH). The separation of Ac from REE is researched, as well as some separation possibilities of the elements within the REE. The determined distribution coefficients allows the prediction of the elution profiles of the researched elements. Using the obtained results in this work further applications can be considered.     

Extraction of lanthanides(III) from Perchlorate Solutions with Carbamoyl- and Phosphorylmethoxymethylphosphine Oxides and Tetrabutyldiglycolamide

The solvent extraction of Ln(III) ions from perchlorate aqueous solutions into an organic phase containing neutral polyfunctional organophosphorus ligands R₂P(O)CH₂OCH₂C(O)NBu₂ R = Bu (I), R = Ph (II) and R₂P(O)CH₂OCH₂P(O)R¹₂ R = R¹ = Bu (III); R = Bu, R¹ = Ph (IV); R = R¹ = Ph(V) has been studied. Their extraction behavior was compared with that of tetrabutyldiglycolamide (TBDGA), tetrabutylmethylenediphosphine dioxide (VI), P,P-dibutyl-P’P’-diphenylmethylenediphosphine dioxide (VII), tetraphenylmethylenediphosphine dioxide (VIII), dibutyl-N,N-dibutylcarbamoylmethylphosphine oxide (IX) and diphenyl-N,N-dibutylcarbamoylmethylphosphine oxide (X). The extraction equilibrium was investigated, and the equilibrium constants were calculated. It was found that the lanthanide(III) ions are extracted with the studied extractants from perchlorate solutions as LnL₃(ClO₄)₃ complexes. In the NaClO₄ media, TBDGA was found to possess a higher extraction efficiency towards Ln(III) ions than other neutral donor ligands studied. A successive replacement of the C(O)NBu₂ groups in the diglycolamide extractant molecule by phosphoryl ones leads to a decrease in the extraction efficiency of Ln(III) ions. In the NaClO₄ media, compounds II, IV and V with phenyl radicals at the P(O) group demonstrate a lower extraction efficiency towards Ln(III) ions than their butyl-substituted analogs. In contrast, phenyl-substituted diphosphine dioxides VIII, VII and carbamoylmethylphosphine oxide (X) extract Ln(III) ions more effectively than their butyl-substituted analogs VI and IX. The extraction of Ln(III) ions from HClO₄ solutions is accompanied by HClO₄ interaction with neutral donor extractants, which leads to a decrease of the free extractant concentration in the organic phase. By this reason, an increase in the HClO₄ concentration higher than 0.1 M is accompanied by a decrease of the Ln(III) extraction with TBDGA. In the 3 M HClO₄ system, diphosphine dioxide VIII outperforms TBDGA at the Ln(III) extraction.     

Structural and Catalytic Studies of a Trimethyltin Vanadate Coordination Polymer

The organotin vanadate [Me₃SnVO₃] (1) has been prepared and characterised in the solid state by powder X-ray diffraction (XRD), thermogravimetric analysis, multinuclear magic-angle spinning (MAS) NMR, IR and Raman spectroscopy. The phase purity and structure of microcrystalline 1 were confirmed by carrying out a full Rietveld structural refinement at ambient temperature and from conventional powder XRD. ⁵¹V and ¹¹⁹Sn MAS NMR data for compound 1 were in agreement with the predicted structure, showing two equally-abundant, nonequivalent Me₃Sn groups and two equally-abundant, nonequivalent vanadium atoms. The compound was applied as a catalyst for the liquid-phase epoxidation of olefins at 55 °C using tert-butyl hydroperoxide (tBuOOH) as the oxidant. The reaction rate for the different substrates followed the order cis-cyclooctene > (R)-(+)-limonene ≅ trans-2-octene > cyclododecene > styrene > 1-octene; the corresponding epoxides were the only observed products. Leaching tests indicated that the catalytic epoxidation of cyclooctene was mainly heterogeneous in nature. This paper is dedicated to Professor Ian Manners and his scientific accomplishments.     

Characterization of biodegradable polymers by inverse gas chromatography. II. Blends of amylopectin and poly(ε‐caprolactone)

Amylopectin (AP), a potato‐starch‐based polymer with a molecular weight of 6,000,000 g/mol, was blended with poly(ε‐caprolactone) (PCL) and characterized with inverse gas chromatography (IGC), differential scanning calorimetry (DSC), and X‐ray diffraction (XRD). Five different compositions of AP–PCL blends ranging from 0 to 100% AP were studied over a wide range of temperatures (80–260°C). Nineteen solutes (solvents) were injected onto five chromatographic columns containing the AP–PCL blends. These solutes probed the dispersive, dipole–dipole, and hydrogen‐bonding interactions, acid–base characteristics, wettability, and water uptake of the AP–PCL blends. Retention diagrams of these solutes in a temperature range of 80–260°C revealed two zones: crystalline and amorphous. The glass‐transition temperature (T_g) and melting temperature (T_m) of the blends were measured with these zones. The two zones were used to calculate the degree of crystallinity of pure AP and its blends below T_m, which ranged from 85% at 104°C to 0% at T_m. IGC complemented the DSC method for obtaining the T_g and T_m values of the pure AP and AP–PCL blends. These values were unexpectedly elevated for the blends over that of pure AP and ranged from 105 to 152°C for T_g and from 166 to 210°C for T_m. The T_m values agreed well with the XRD analysis data. This elevation in the T_g and T_m values may have been due to the change in the heat capacity at T_g and the dependence of T_g on various variables, including the molecular weight and the blend composition. Polymer blend/solvent interaction parameters were measured with a variety of solutes over a wide range of temperatures and determined the solubility of the blends in the solutes. We were also able to determine the blend compatibility over a wide range of temperatures and weight fractions. The polymer–polymer interaction coefficient and interaction energy parameter agreed well on the partial miscibility of the two polymers. The dispersive component of the surface energy of the AP–PCL blends was measured with alkanes and ranged from 16.09 mJ/m² for pure AP to 38.26 mJ/m² when AP was mixed with PCL in a 50/50% ratio. This revealed an increase in the surface energy of AP when PCL was added. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3076–3089, 2006     

Analysis of the polyethylene glycol glucosides and FA esters thereof by atmospheric-pressure ionization MS

Polyethylene glycol (PEG) glucosides (PEGG) and the PEGG esters of lauric acid were analyzed by atmospheric-pressure ionization MS (API-MS) with electrospray ionization. Straightforward mass characterization of the complex mixtures could be achieved without prior chromatographic separation. The constituents were identified on the basis of quasi-molecular ions. Individual components could be observed as protonated molecular ions [M+H]⁺ and/or as their NH₄ ⁺, Na⁺, or K⁺ adducts in positive ion mode. The mass spectrometric investigation showed that mixtures of PEGG consisted of monoglucoside, diglucoside, polyglucoside, and free PEG. The esterification product is a mixture of two types of nonionic surfactants: PEG-laurates and PEGG-laurates. The reasons for distortion of the quasi-molecular ion intensities and the stabilization of adduct ions were discussed. The rapid and highly sensitive API-MS analysis technique proposed here is well suited for direct characterization of complex mixtures and suitable for development as a routine analytical method.     

Homonuclear tris-dithiocarbamato ruthenium(III) complexes as single-molecule precursors for the synthesis of ruthenium(III) sulfide nanoparticles

Tris(N-phenyldithiocarbamato) ruthenium(III) complexes, [Ru(L¹)₃] (1); tris(N-(4-methylphenyl)dithiocarbamato)) ruthenium(III), [Ru(L²)₃] (2); and tris(N-(4-methoxyphenyl)dithiocarbamato)) ruthenium(III), [Ru(L³)₃] (3) were synthesized and characterized by elemental analysis, thermogravimetric analysis, FTIR, UV–VIS and NMR spectroscopy. TGA analyses show major degradation of all complexes in the range 120–350°C, leading to the formation of residual weight corresponding to ruthenium (III) sulfides. The ¹H-NMR spectra of the ligands and complexes are in agreement with the proposed structures. FTIR studies confirmed that the ligands coordinate the Ru³⁺ ion in a bidentate chelating mode. The complexes were thermolysed at 180°C to prepare hexadecylamine-capped Ru₂S₃ nanoparticles. Powder X-ray diffraction patterns revealed the formation of hexagonal-phase Ru₂S₃ nanoparticles with average crystallite sizes ranging from 8.3 to 9.5?nm. TEM images showed the crystalline clusters with shapes ranging from square to hexagonal, while SEM images elucidated that the particles were agglomerated. Energy-dispersive X-ray spectra confirmed the presents of Ru₂S₃ nanoparticles.     

Negative air ion releasing properties of tourmaline/bamboo charcoal compounds containing ethylene propylene diene terpolymer/polypropylene composites

The average concentrations of negative air ions (C_ion?) emitted from tourmaline (T), bamboo charcoal (B) particles, and tourmaline/bamboo charcoal (T/B) compounds containing polypropylene (PP) and ethylene propylene diene terpolymer/polypropylene (EPDM/PP) composite specimens under varying testing conditions were investigated in this study. The C_ion? values emitted from T or B filled PP and EPDM/PP composite specimens reached a maximum value as their T or B contents approached the 5 and 3 wt % optimum values, respectively. In contrast, the C_ion? values of T/B compounds filled PP and EPDM/PP composite specimens were significantly higher than their theoretical C_ion? values estimated using the “simple mixing rule,” and reached a maximum value as the weight ratio of T to B reaches an optimum value. At this optimum T/B weight ratio, the C_ion? values of T/B compounds filled PP and EPDM/PP composite specimens reached another maximum as their total compound loadings reached the optimum loading of 6 and 4 wt %, respectively. The C_ion? values of the PP/T/B and EPDM/PP/T/B specimens increased significantly as they were tested under dynamic mode or by increasing the testing temperatures. The T and/or T/B powders filled PP and EPDM/PP specimens exhibited significantly higher tensile strength (σ_f) and elongation at break (ε_f) values than did the B filled PP and EPDM/PP specimens with the same filler loadings, respectively. Energy dispersive X‐rays, particle size, and SEM morphology analysis of the filler particles present in the T, B, and T/B filled composite specimens were performed to understand these interesting negative air ion and tensile properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A Simple Electrostatic Model for the Chromatographic Behavior of the Primary Dithizonates

Abstract

A simple electrostatic model of the reactive sites of primary metal dithizonates which fits their published chromatographic behavior is described. Coordination with a metal ion tends to increase the formal charge on the hindered imino hydrogens in the molecule. This increase is a function of the individual metal's Sanderson electronegativity. Plots of R _m vs. electronegativity are rectilinear, have the same form for all systems and adsorbents described, and place dithizonates of similar molecular geometry on separate curves. The results of this study suggest that the dithizonates are a heterogeneous group of compounds which differ in coordination configuration and geometry.     

Determination of polymer–polymer interaction parameters using inverse gas chromatography

A modified method is discussed that is based on Farooque and Deshpande's method to obtain polymer–polymer interaction parameters using inverse gas chromatography (IGC) data. In the Farooque and Deshpande method, the ratio of the difference of probe–polymer interaction parameters between two polymers and the probe volume [(χ₁₂ ? χ₁₃)/V₁] is used as the abscissa. In the modified method, the ratio [(?₂χ₁₂ + ?₃χ₁₃)/V₁] is used as the abscissa. Experimental data previously reported for a poly(?‐caprolactone)‐polyepichlorohydrin (PCL/PECH) blend and a poly(ethyl acrylate)‐poly(vinyl propionate) (PEA/PVPr) blend are analyzed. It is found that the slopes obtained by the new method had smaller deviations from the theoretical values than the Farooque and Deshpande method. The standard deviations of both slopes and intercepts obtained from the new method are also smaller. Using the new method, the polymer–polymer interaction parameters obtained from the intercept are negative numbers for the PCL/PECH system and very small positive numbers for PEA/PVPr. Explanations are given for the probe and concentration dependency of the polymer–polymer interaction parameters that are generally observed in IGC studies. A new method for selecting the best probe for calculating the interaction parameter is discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 671–680, 2003