Nonmonotonic pattern of the critical percolation temperature due to variations of additive chain length in water-in-oil microemulsions

The nonmonotonic variation of the critical percolation temperature (T _c) of ternary nonionic (C₁₄E₅) water-in-oil microemulsions was studied as a function of the alkyl chain length of an ionic additive (n-alkyl sulfonate sodium salt). A thermodynamic approach shows the relationship between T _c and additive chain length, which is supplemented by a consideration of a possible molecular mechanism of the observed phenomenon. Received: 20 October 2000 Accepted: 7 November 2000     

Synthesis and properties of nonylphenol-substituted dodecyl sulfonate

Nonylphenol-substituted dodecyl sulfonate (C₁₂-NPAS) was synthesized via sulfonation-alkylation-neutralization using 1-dodecene, SO₃, and nonylphenol as raw materials. The properties such as surface tension, interfacial tension (IFT), wettability, foam properties, and salinity tolerance of C₁₂-NPAS were systematically investigated. The results show that the critical micelle concentration (CMC) of C₁₂-NPAS was 0.22?mmol?·?L^?1 and the surface tension at the CMC (γ_CMC) of C₁₂-NPAS was 29.4 mN/m. When compared with the traditional surfactants sodium dodecyl benzene sulfonate (SDBS), sodium dodecyl sulfate (SDS), and linear alkylbenzene sulfonate (LAS), the surface properties of C₁₂-NPAS were found to be superior. The IFT between Daqing crude oil and a weak-base alkaline/surfactant/polymer (ASP) oil flooding system containing 0.1?wt% of C₁₂-NPAS can reach an ultralow level of 2.79?×?10^?3 mN/m, which was lower than that found for the traditional surfactant heavy alkylbenzene sulfonate (HABS). The salinity and hardness tolerance of C₁₂-NPAS were much stronger than those found for conventional surfactants, petroleum sulfonate, and LAS. C₁₂-NPAS also shows improved wetting performance, foamability, and foam stability.     

Random homogeneous sodium sulfonate polysulfone ionomers: Preparation,characterization, and blend studies

The sodium salts of randomly sulfonated polysulfone (Na-SPSF), derived from 1,1′-sulfonylbis-[4-chlorobenzene] with 4,4′-(1-methylethylidene)-bis-[phenol], were prepared over the composition range of 3–30 mol% sodium sulfonate, using improved procedures in which the sulfonating complex was introduced into an intensely agitated polymer solution. In contrast to earlier work, T_g was found to increase nonlinearly with sodium sulfonate content. A SAXS study provided no evidence of ionic clustering in these polymers. Binary blends of Na-SPSFs differing only in composition were prepared by casting films from solution, and their phase behavior was studied by dynamic mechanical analysis after annealing at 250°C. It was found that the blends were miscible up to a composition difference of about 9–10 mol% sodium sulfonate. Using this fact it was possible to calculate a value for χ_ABn of 200–250, where χ_AB represents the segmental interaction parameter between unmodified and modified repeat units, and n is the degree of polymerization. Uncertainty in the degree of ionic association places a degree of uncertainty on the effective value of n and therefore on χ_AB. The product, however, is independent of any assumptions regarding molecular associations.     

Infrared investigation of the silicon oxide phase in [perfluoro-carboxylate/sulfonate (bilayer)]/[silicon oxide] nanocomposite membranes

[Perfluoro-organic]/[silicon oxide] hybrids were formed by conducting sol-gel reactions of tetraethylorthosilicate within a perfluoro(carboxylate/sulfonate) bilayer membrane in the Co⁺² form. FTIR and ²⁹Si solid-state NMR spectroscopies were used to probe general aspects of molecular structure within the silicon oxide phase as a function of its relative content. The internal gel structure is considerably unconnected in terms of the population of Si O Si groups in cyclic vs. linear substructures and degree of Si atom coordination about bonded SiO₄ units. In situ (HO)_xSiO_2[1-1/4x] intrastructure become increasingly less connected and more strained with regard to bonding geometry with increasing percent silicon oxide. Structural differences are seen between the silicon oxide component incorporated in carboxylate and sulfonate layers. These inorganically modified perfluorinated ionomers have potential as fast-proton conducting membranes for fuel cells and as permselective membranes in liquid pervaporation cells. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 595–606, 1998     

Comparisons of styrene ionomers prepared by sulfonating polystyrene and copolymerizing styrene with styrene sulfonate

As part of a continuing study of ion-containing polymers, a comparison has been made on styrene-based sulfonate ionomers obtained by two different processes. Copolymers of styrene with sodium styrene sulfonate (SSS) have been compared with corresponding polymers obtained by the sulfonation/neutralization of preformed polystyrene (S–PS). The former system covered a range of sulfonate level from 1 to 30 mol %, while the latter ranged from about 1 to 7 mol %. The characterization of these materials has been conducted using solubility behavior, dilute solution viscometry, thermal mechanical analysis, density measurements, and water adsorption studies. At low (ca. 1%) levels the solubility behavior of the SSS copolymers and the sulfonated polystyrenes were similar. However, at higher sulfonate levels the solubility behavior in different solvents and the dilute solution viscometry were significantly different for the two systems. Similarly, thermal analysis studies (DSC) showed that the glass transition of the sulfonated polystyrene increased linearly with sulfonate level, while the T_g for the SSS copolymer increased modestly, up to about 7 mol % sulfonate content, and then remained constant. Significant differences in the softening behavior and water absorption characteristics were also observed for these two classes of ionomers. Although molecular weights and molecular weight distributions are not now available for these ionomers, the differences in their behavior does not appear to be due simply to differences in molecular weight. It is postulated that the differences in the copolymer and the S–PS ionomers may originate with differences in sulfonate distribution. It is suggested that the SSS monomer units are incorporated as blocks in the copolymer as opposed to a more random distribution in the S–PS ionomer. Indirect evidence in support of his argument is found, for example, in the case of the copolymer in the solubility behavior, the relative independence of T_g on sulfonate concentration and the apparent existence of a second, high temperature transition tentatively attributable to an ion-rich phase. Additional studies are required to confirm this hypothesis.     

Poly­[disilver(I)‐μ8‐1,5‐naphthalene­disulfonato]

The title complex, poly­[disilver(I)‐μ₈‐1,5‐naphthalene­di­sulfon­ato‐3,4‐η:7,8‐η:κ⁶O:O′:O′′:O′′′:O′′′′:O′′′′′], [Ag₂(C₁₀H₆O₆S₂)]_n, exists as a three‐dimensional framework of Ag^I atoms connected by η¹⁰,μ₈‐1,5‐naphthalene­di­sulfonate ligands through both Ag–sulfonate and Ag–η²‐arene interactions. Each Ag^I atom exhibits a distorted tetrahedral geometry defined by three O atoms of independent sulfonate groups and one C=C bond of the naphthalene group.     

Synthesis of poly(vinylidene fluoride)‐b‐poly(styrene sulfonate) block copolymers by controlled radical polymerizations

Block copolymers based on poly(vinylidene fluoride), PVDF, and a series of poly(aromatic sulfonate) sequences were synthesized from controlled radical polymerizations (CRPs). According to the aromatic monomers, appropriate techniques of CRP were chosen: either iodine transfer polymerization (ITP) or atom transfer radical polymerization (ATRP) from PVDF‐I macromolecular chain transfer agents (CTAs) or PVDF‐CCl₃ macroinitiator, respectively. These precursors were produced either by ITP of VDF with C₆F₁₃I or by radical telomerization of VDF with chloroform, respectively. Poly(vinylidene fluoride)‐b‐poly(sodium styrene sulfonate), PVDF‐b‐PSSS, block copolymers were produced from both techniques via a direct polymerization of sodium styrene sulfonate (SSS) monomer or an indirect way with the use of styrene sulfonate ethyl ester (SSE) as a protected monomer. Although the reaction led to block copolymers, the kinetics of ITP of SSS showed that PVDF‐I macromolecular CTAs were not totally efficient because a limitation of the CTA consumption (56%) was observed. This was probably explained by both the low activity of the CTA (that contained inefficient PVDF‐CF₂CH₂? I) and a fast propagation rate of the monomer. That behavior was also noted in the ITP of SSE. On the other hand, ATRP of SSS initiated by PVDF‐CCl₃ was more controlled up to 50% of conversion leading to PVDF‐b‐PSSS block copolymer with an average number molar mass of 6000 g·mol^?1. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

A liquid crystal derived from ­ruthenium(II,III) and a long‐chain carboxylate

The title compound, catena‐poly[[tetrakis(μ‐decanoato‐κ²O:O′)diruthenium(II,III)(Ru—Ru)]‐μ‐octanesulfonato‐κ²O:O′], [Ru₂(C₁₀H₁₉O₂)₄(C₈H₁₇O₃S)], is an octane­sulfonate derivative of the mixed‐valence complex diruthenium tetradecanoate. The equatorial carboxyl­ate ligands are bidentate, bridging two Ru atoms to form a dinuclear structure. Each of the two independent dinuclear metal complexes in the asymmetric unit is located at an inversion centre. The octane­sulfonate anion bridges the two dinuclear units through axial coordination. The alkyl chains of the carboxyl­ate and sulfonate ligands are arranged in a parallel manner. The global structure can be seen as infinite chains of polar moieties separated by a double layer of non‐polar alkyl groups, without interdigitation of the alkyl chains.     

Striking differences between alkyl sulfate and alkyl sulfonate when mixed with cationic surfactants

The properties of alkyl sulfate and alkyl sulfonate are similar except for their Krafft points. However, alkyl sulfate and alkyl sulfonate behave quite differently when they are mixed with cationic surfactants and show some totally unexpected results. In this work sodium alkyl sulfate (C_nH_2n+1SO₄Na,C_nSO₄)–alkyl quaternary ammonium bromide [C_nH_2n+1N(C_mH_2m+1)₃Br, C_nN, m=1–4] mixtures and sodium alkyl sulfonate (C_nH_2n+1SO₃Na, C_nSO₃)–C_nN mixtures were studied. It was found that, in contrast to the single surfactants, C_nSO₃–C_nN mixtures were much more soluble than C_nSO₄–C_nN mixtures. Besides, the two kinds of catanionic surfactant mixtures were quite different in their phase behavior and aggregate properties. The results were interpreted in terms of the interactions between surfactant molecules, which were very different in the two kinds of mixed systems owing to the distinction between alkyl sulfate and alkyl sulfonate in the molecular charge distribution.     

3‐(1‐Pyridinio)propane­sulfonate and 3‐(benzyl­dimethyl­ammonio)propane­sulfonate monohydrate

3‐(1‐Pyridinio)propane­sulfonate, C₈H₁₁NO₃S, and 3‐(benzyl­dimethyl­ammonio)propane­sulfonate monohydrate, C₁₂H₁₉NO₃S·H₂O, used as additives during protein refolding and crystallization, both crystallize in the monoclinic system in the P2₁/c space group, with one mol­ecule (or one set of mol­ecules) per asymmetric unit. The solvent water mol­ecule present in the second crystal structure results in the formation of a dimer through hydrogen bonds. The conformation of the propane­sulfonate moiety is similar in both structures.     

Polymeric sodium 3,5‐di­carboxy­benzene­sulfonate–urea–water (1/1/1)

In the title compound, poly­[sodium‐μ₄‐3,5‐di­carboxy­benzene­sulfonato‐κ⁴O:O′:O′′:O′′′‐μ₂‐urea‐κ²O:N] monohydrate], {[Na(C₈H₅O₇S)(CH₄N₂O)]·H₂O}_n, the organic anions are arranged almost vertically within (001) monolayers, with the sulfonate and carboxylic acid groups pointing into the interlayer region. The inversion‐related aromatic rings of the anions inside the layers are arrayed via offset face‐to‐face interactions into molecular stacks along the crystallographic a axis. The `up' and `down' arrangement of the aromatic portions makes both faces of the layers ionic and hydro­philic, whereas the interiors of the layers are primarily hydro­phobic. The interleaving of the anions is such that the carboxylic acid groups are oriented more toward the interior than are the sulfonate groups. The aromatic rings in neighbouring layers are arranged in a herring‐bone fashion. The coordination sphere of the Na⁺ ions contains two sulfonate and two carboxylic acid O atoms, from a total of four different acid anions belonging to two neighbouring anionic monolayers. The urea mol­ecules are positioned between translation‐related anionic stacks inside the (001) layers, serving a triple function, viz. they fill in the large meshes (empty cavities) formed within the anionic–cationic network, and they provide additional Na⁺ coordination and hydrogen‐bond sites.     

Effect of an anionic emulsifier on the structure of butadiene-nitrile elastomers

X-ray diffraction and TMA studies show that surfactant sodium alkyl sulfonate (C₁₅) forms one of its two LC structures (distinguished by the smallest layer periodicity) in butadiene-nitrile elastomers containing different amounts of acrylonitrile units. In this case, the surfactant serves as a structural plasticizer and facilitates a more complete selective segregation of microblocks of trans-1,4-butadiene units and, especially, of sequences of alternating trans-1,4-butadiene and acrylonitrile units.     

Diaquabis(propane-1,2-diamine-N,N′)nickel(II) bis(p-toluenesulfonate)

The crystal structure of the title compound, [Ni(C₃H₁₀N₂)₂(H₂O)₂](C₇H₇O₃S)₂ or [Ni(H₂O)₂{NH₂CH₂CH­(NH₂)CH₃}₂](CH₃C₆H₄SO₃)₂, exhibits a layered structure in which the complex cations and the p-toluene­sulfonate anions form alternating layers. The central Ni^II atom of the cation resides on a crystallographic inversion centre and has a slightly distorted octahedral coordination composed of the water ligands bonding through oxy­gen in a trans arrangement and the N,N′-bidentate propane­di­amine ligands. The p-toluene­sulfonate anions are arranged with the sulfonate groups turned alternately towards opposite sides of the layers. The structure of the layers is stabilized by a network of hydrogen bonds between the sulfonate O atoms, water mol­ecules and the propane­di­amine N atoms.     

Sulfonate pseudohalides of boron subphthalocyanine

The crystal structures of three sulfonate pseudohalide derivatives of boron subphthalocyanine (BsubPc) are described and compared with four structures of three published sulfonate derivatives. Benzenesulfonate boron subphthalocyanine [(benzenesulfonato)(subphthalocyaninato)boron, C₃₀H₁₇BN₆O₃S, (I)] crystallizes in the space group P with Z = 2. The structure contains two centrosymmetric π‐stacking interactions between the concave faces of the isoindoline units in the BsubPc ligands. 3‐Nitrobenzenesulfonate boron subphthalocyanine [(3‐nitrobenzenesulfonato)(subphthalocyaninato)boron, C₃₀H₁₆BN₇O₅S, (II)] crystallizes in the space group P2₁/c with Z = 4. The structure contains an intermolecular S—O...π interaction from the sulfonate group to a five‐membered N‐containing ring of an isoindoline unit on the concave side of a neighbouring BsubPc ligand, at a distance of 3.151 (3) Å. The crystal of methanesulfonate boron subphthalocyanine [(methanesulfonato)(subphthalocyaninato)boron, C₂₅H₁₅BN₆O₃S, (III)] was produced via sublimation and it is not a solvate, in contrast with two previously published structures of the same compound. Compound (III) crystallizes in the space group P2₁/n with Z = 2, and its structure is similar to that of the more common compound Cl‐BsubPc.     

Sodium trichloro­methane­sulfonate monohydrate

Sodium trichloro­methane­sulfonate monohydrate, Na⁺·CCl₃SO₃⁻·H₂O, crystallizes in P2₁/a with all the atoms located in general positions. The trichloro­methane­sulfonate (trichlate) anion consists of pyramidal SO₃ and CCl₃ groups connected via an S—C bond in a staggered conformation with approximate C_3v symmetry. The water mol­ecule is hydrogen bonded to the sulfonate O atoms, with one water H atom forming weak bifurcated O—H⋯O hydrogen bonds to two different trichlate ions. Two water O atoms and three O atoms from different SO₃ groups form a square‐pyramidal arrangement around the sodium ion.     

The effects of substitution on tetrakis­(substituted imidazole)­copper(II) tri­fluoro­methane­sulfonates

The organic ligands 4‐methyl‐1H‐imidazole and 2‐ethyl‐4‐methyl‐1H‐imidazole react with Cu(CF₃SO₃)₂·6H₂O to give tetrakis(5‐methyl‐1H‐imidazole‐κN³)­cop­per(II) bis­(tri­fluoro­methane­sulfonate), [Cu(C₄H₆N₂)₄](CF₃SO₃)₂, and aqua­tetrakis(2‐ethyl‐5‐methyl‐1H‐imidazole‐κN³)copper(II) bis(tri­ fluoro­methane­sulfonate), [Cu(C₆H₁₀N₂)₄(H₂O)](CF₃SO₃)₂. In the former, the Cu atom has an elongated octahedral coordination environment, with four imidazole rings in equatorial positions and two tri­fluoro­methane­sulfonate ions in axial positions. This conformation is similar to those in the analogous complexes tetrakis­(imidazole)­cop­per(II) tri­fluoro­methane­sulfonate and tetrakis(2‐methyl‐1H‐imidazole)­cop­per(II) tri­fluoro­methane­sulfonate. In the second of the title compounds, the ethyl groups block the central Cu atom, and a square‐pyramidal coordination environment is formed around the Cu atom, with the substituted imidazole rings in the basal positions and a water mol­ecule in the axial position.     

Superacid polymers from sulfonated poly(styrene-divinylbenzene): Preparation and characterization

Superacid polymers were prepared by bringing metal halides (AlCl₃, SnCl₄, TiCl₄, BF₃, or SbF₅) in contact with macroporous sulfonic acid resins [sulfonated, crosslinked poly(styrene-divinylbenzene)]. The resulting solids were characterized by chemical analysis, temperature-programmed desorption, transmission electron microscopy, and X-ray photoelectron spectroscopy. They were also tested as catalysts for n-butane isomerization at 0.5 bar and 60 to 120°C. The polymers consist of supported metal oxyhalide particles, complexes of metal oxyhalides and sulfonate groups, and the remaining unreacted sulfonic acid groups. In the presence of HCl, these polymers were highly active catalysts for the butane isomerization reaction, the activity being a consequence of a high proton-donor strength inferred to be associated with H₂Cl⁺ groups stabilized on the polymer surface by negative charge delocalization over sulfonate–metal oxyhalide sulfonate groups.     

Bis(β-alaninium) biphenyl-4,4′-disulfonate

In the crystal structure of the title compound, 2C₃H₈NO₂⁺·C₁₂H₈O₆S₂²⁻, N—H⃛O hydrogen bonds formed between the amino H atoms and the sulfonate O atoms give rise to the assembly of cationic β-alaninium dimers and centrosymmetric bi­phenyl-4,4′-­di­sulfonate anions into an extended two-dimensional layer. The resulting hydrogen-bonded ribbons can be described as C(6)R(12) according to graph-set notation. C—H⃛O hydrogen bonds between adjacent sheets further extend the structure into a three-dimensional arrangement.     

The sodium salt of 2‐hydroxy‐5‐nitrobenzylsulfonic acid

The structural data for sodium 2‐hydroxy‐5‐nitro­benzyl­sulfonate monohydrate, Na⁺·C₇H₆NO₆S^?·H₂O, which mimics an artificial substrate for human aryl­sulfatase A, viz. p‐­nitrocatechol sulfate, reveal that the geometric parameters of the substrate and its analogue are very similar. Two water mol­ecules, the phenolic O atom and three sulfonate O atoms form the coordination sphere of the Na⁺ ion, which is a distorted octahedron. The Na⁺ cations and the O atoms join to form a chain polymer.     

Bis-dioxomolybdenum (VI) oxalyldihydrazone complexes: Synthesis,characterization, DFT studies,catalytic epoxidation potential,molecular modeling and biological evaluations

Two cis-bis-dioxomolybdenum oxalylsalicylidenedihydrazone complexes (MoO₂L1 and MoO₂L2) were synthesized via the complexation of dioxomolybdenum (VI) acetylacetonate with oxalylsalicylidenedihydrazone (H₂L1) and p-sodium sulfonate oxalylsalicylidenedihydrazone (H₂L2) bis-Schiff base chelating ligands, respectively. The structures of the newly synthesized complexes were confirmed by ¹H- and ¹³C-NMR, IR, ultraviolet–visible and mass spectra, as well as elemental analyses (EA) and conductivity measurements. The spectrophotometric continuous variation method revealed the formation of 2: 1 (metal: ligand molar ratios). DFT studies were applied for the ligands and their Mo-chelates. Interestingly, the bis-MoO₂(VI) oxalyldihydrazone complexes showed remarkable catalytic sufficiency towards the selective (ep)oxidation of 1,2-cyclooctene, benzyl alcohol and thiophene using H₂O₂ or tert-butyl hydroperoxide (tBuOOH) at 85 °C. Under aqueous conditions, the MoO₂L2 (with p-sodium sulfonate substituent) exhibited superior that of the MoO₂L1 (without p-NaSO₃―group), highlighting the role of sodium sulfonate substituent in the catalytic progress of the Mo-chelate. The ligands (H₂L1 and H₂L2) and their corresponding Mo-complexes (MoO₂L1 and MoO₂L2) were assessed for their antitumor and antimicrobial activities. Furthermore, the antioxidant activity was also evaluated using the 2,2-diphenyl-1-picrylhydrazyl (DPPH) and superoxide dismutase (SOD) assays. The binding nature between the Mo-complexes and calf thymus DNA (ctDNA) was also studied within spectroscopic and hydrodynamic techniques.