Surface and interfacial FTIR spectroscopic studies of latexes. IV. The effect of surfactant structure on the copolymer–surfactant interactions

The interactions between sodium dodecylbenzene sulfonate (SDBS) and the components of an ethyl acrylate/methacrylic acid (EA/MAA) copolymer latex were examined and the influences of using D₂O as the synthetic suspension medium were investigated. Whereas it is found that D₂O has no detectable influence on the fully coalesced latex films, the film coalescence conditions are shown to significantly affect the nature of surfactant interactions within the film matrix. When films are prepared and stored under controllable low atmospheric water-vapor concentrations, hydrogen-bonding interactions between the surfactant SO₃^?Na⁺ groups and the copolymer acid functionality dominate. However, coalescence and storage of the films under higher relative humidity conditions results in a displacement of these interactions in favor of the hydrated form of the surfactant. It is also shown that the presence of an aromatic ring adjacent to the surfactant sulfonate group exerts an influence on the nature of the SO₃^? ··· HOOC interactions within the copolymer matrix. Relative to sodium dioctyl sulfosuccinate (SDOSS), the aromatic group near hydrophilic end of SDBS increases the strength of the S? O bond in the presence of acid interactions. © 1993 John Wiley & Sons, Inc.     

Fundamental study of biochemical behavior of anionic sulfonate- and sulfate-type surfactants

The interactions of α-olefin sulfonate with proteins were studied and a few environmental and hygienic phenomena investigated on the basis of these interactions. It was found that α-olefin sulfonate formed a complex with proteins mainly through ionic bonds similar to those formed by linear alkylate sulfonate and alkyl sulfate and that the α-olefin sulfonate-protein complex had much in common with these surfactant-protein complexes. The data on surfactant adsorption indicate that the effects of sulfonate-type surfactants are due to the formation of complexes with the protein of the skin, hog bristles, and human hair. Adsorption of surfactant occurred in the gills of fish; the adsorption increased with time. When protein was added, the surfactant solution was less biologically effective to fish. The data suggest that adsorption of the surfacntant disturbs the functions of fish gills. Increase in erythrocyte count, which always is found in oxygen-deficient conditions, occurred in fish killed by exposure to the surfactant.     

Miscibility and interactions in polystyrene and sodium sulfonated polystyrene with poly(vinyl methyl ether) PVME blends. Part II. FTIR

The miscibility and specific interactions of polystyrene (PS) and sodium sulfonated polystyrene (Na-SPS) with poly(vinyl methyl ether) (PVME) blends (ranging from 10 to 90% PS by weight) were examined experimentally by FTIR spectroscopy. The FTIR studies at different temperatures have shown that changes in spectra of polymer blends, as reported in the literature can be explained by temperature changes in pure homopolymers. This indicates that molecular interactions, which are responsible for miscibility, are not detectable by infrared absorptions and are therefore of unspecific strength and location. The FTIR of SPS/PVME blends show that sulfonate groups of PS affect polymer miscibility through changes in configuration of molecules, rather than through direct interaction with the PVME.     

新型表面活性剂、助剂与碱性蛋白酶的相互作用

研究了洗涤剂组分中表面活性剂(MEE、AEC、甜菜碱、AEO9、AOS、LAS)溶液和助剂(高稳定层状二硅酸钠、3型AN助剂、亚微米4A沸石、4A沸石)溶液对碱性蛋白酶(黄海黄杆菌YS-9412-130低温碱性蛋白酶、Properase450E、Savinase4.0T)的影响作用。40min时表面活性剂溶液中酶的存活率在70%以上,助剂中酶的存活率在85%以上,并对以上结果提出可能的作用机理解释。     

Partitioning of o/p-Nitrophenols in the Presence of Hydrotropes in Aqueous Solutions

Abstract

Partitioning of o/p-nitrophenols between organic solvents and water in the presence of hydrotropes such as sodium toluene sulfonate, sodium xylene sulfonate, and sodium cumene sulfonate, has been experimentally investigated and modelled in terms of co-aggregation of the hydrotrope and nitrophenols in aqueous solutions. The phenol-hydrotrope and hydrotrope-hydrotrope interactions are characterized by an aggregation model. The experimental data for a series of hydrotropes are further used to predict the partitioning behavior of p-nitrophenol in the presence of sodium butyl benzene sulfonate (Na-NBBS). The aggregation number of NaNBBS, (～30) obtained from the partitioning data, matches well with that obtained by small angle neutron scattering.     

Structure–property relationships for sulfonated poly(butylene terephthalate)

Structure–property relationships have been developed for sulfonated poly(butylene terephthalate) copolymers. The compositional variables investigated were sulfonate content, molecular weight, and polymer endgroup composition, and the fundamental polymer properties evaluated were melt viscosity, crystallization kinetics, and impact strength. It was found that all compositional variables significantly affect all of the polymer properties of interest. The most interesting effect is the influence of polymer endgroup composition on polymer properties. The trends indicate that the carboxylic acid endgroups form intermolecular interactions with sodium sulfonate groups, resulting in a decrease in the strength of intermolecular ionic interactions between sodium sulfonate groups. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4662–4771, 2006     

Nanocomposites based on polyethylene and Mg-Al layered double hydroxide. I. Synthesis and characterization

Low density polyethylene (LDPE)/Mg-Al layered double hydroxide (LDH) nanocomposites have been synthesized with different compositions by melt-mixing technique using maleic anhydride grafted polyethylene as compatibilizer. LDH has been modified by sodium dodecylbenzene sulfonate using reconstruction method and characterized by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. The nanocomposites are characterized by different techniques such as, transmission electron microscopy (TEM), XRD and rheology. The TEM analysis shows a complex nature of particle dispersion in the polymer matrix with wide distribution of particles sizes and shapes. The rheological analysis showed significant changes in linear viscoelastic responses of the composites, even at very low concentration (2 phr) of LDH materials, in comparison to the pure polymer in low frequency regime in dynamic frequency sweep experiments. These changes are related to the LDHs-polymer chains interactions resulting in network-like structure.     

Time-dependent characteristics of sulfonated EPDM containing zinc stearate. I. Thermal behavior

The crystallization and melting of zinc stearate (ZnSt) in ZnSt-plasticized compositions of ethylene–propylene–diene terpolymer (EPDM) and sulfonated EPDM (S-EPDM) have been studied by differential scanning calorimetry. While immiscible in both EPDM and S-EPDM, ZnSt is compatible with the latter. This compatibility presumably arises from either electrostatic or dipole–dipole interactions between the carboxylate functionality of ZnSt and the sulfonate groups of the polymer. The crystallization behavior of ZnSt is significantly perturbed when the material is added to S-EPDM, and the crystalline ZnSt phase that results is strongly time dependent. ZnSt first crystallizes as small imperfect crystals when the compositions are cooled from the melt, but it eventually anneals at room temperature into larger, more perfect crystals. Time dependent changes in the mechanical properties of these compositions are also demonstrated and it is suggested that this may be due in part to changes in the ZnSt morphology.     

Effects of Chemical Treatments on Ultra-High-Yield Pulping. VI. The Relative Effect of Lignin Oxidation and Sulfonation

The chemical properties and performance of aspen percarbonate (P) and sulfite (S) chemimechanical pulp (CMP) fibers are very comparable. The PCMP, when compared with SCMP of the same yield, has a slightly higher tear index, same beatability and light scattering coefficient, but a lower tensile index and brightness. The strength properties of these fibers are closely related to the total acidic group content resulting from lignin oxidation (carboxyls) and sulfonation (sulfonate).     

Control of ionic interactions in sulfonated polystyrene ionomers by the use of alkyl-substituted ammonium counterions

Polystyrenes containing up to about 20 mol % sulfonic acid are reproducibly and readily prepared by the sulfonation of polystyrene at 50°C with acetyl sulfate in 1,2-dichloroethane solution. The metal salts of sulfonated polystyrene possess extremely high melt viscosities and are soluble in single solvents such as toluene and THF only at very low sulfonate levels. Such properties are the result of the very strong ion-dipole interactions among the metal sulfonate groups. Such strong interactions can be substantially reduced through the neutralization of the sulfonic acid with ammonia and, most especially, relatively simple low molecular weight amines. Sulfonated polystyrenes varying in sulfonic acid content from about 1 mol % to about 20 mol % were neutralized with various mono-, di-, and tri-substituted alkyl amines ranging in alkyl chain length from H (ammonia) to C₂₀, and their rheological and thermal properties were measured. As the number of substituents on the nitrogen increased, the glass transition temperature and the melt viscosity decreased. The tributylamine sulfonates possessed viscosities almost as low as unsulfonated polystyrene and the longer chain amines behaved as if internally plasticized. The properties of amine neutralized sulfonated polystyrenes are concluded to be primarily a function of amine size. Increasing the size of the amine reduces the strength of the ion-dipole interaction by preventing close approach of the amine sulfonate groups.     

Surface and interfacial FTIR spectroscopic studies of latexes. II. Surfactant–copolymer compatibility and mobility of surfactants

Whereas molecular level interactions between sulfonate groups of SDOSS surfactant and COOH groups of EA/MMA copolymer have been discussed in part I of this series, the major focus of this work is to establish the effect of compatibility on the distribution of surfactants at the film–air and the film–substrate interfaces. It is found that the exudation of anionic surfactants is inhibited in neutralized ethyl acrylate/methacrylic acid latex films. On the other hand, nonionic surfactants do not exhibit enrichment at the film interfaces. The inhibited exudation of anionic surfactants is attributed to the increased compatibility resulting from surfactant penetration into the swollen latex particles. This is followed by the formation of solubilized polymer–surfactant complexes through the adsorption of surfactant onto the hydrophobic polymer segments. The effect of neutralization of the carboxylic acid groups on the exudation of anionic surfactants suggests the formation of hydrophobic interactions that overwhelm surface tension effects and prevent surfactant enrichment at either interface.     

Study of the factors determining the mobility of ions in the polypyrrole films doped with aromatic sulfonate anions

The electrochemical redox behavior of the polypyrrole (PPy) films doped with benzenesulfonate (BS), p-toluenesulfonate (pTS) and naphtalene-1,5-disulfonate (NDS) was investigated by cyclic voltammetry, the chemical composition of the films was determined by XDS, the surface morphology was characterized by AFM, and the interactions between pyrrole oligomers and the anions were modeled with quantum chemical methods. It is the first detailed comparative study of the properties of these interesting systems with two complementing interactions (electrostatic and aromatic stacking). It was shown than these relatively similar aromatic sulfonate anions have rather different behavior in PPy films. The results showed that the redoxactivity of polypyrrole films doped with sulfonate ions increases in the sequence pTS < BS < NDS. The comparison of voltammograms measured in the presence of different anions with PPy films synthesized in the same solution show that the PPy/pTS films have the most densely packed and the PPy/NDS films the least densely packed structure of the three. The mobility of ions in these films is mainly determined by the packing of the films, which in turn partly depends on the interactions between the dopant-anion and polymer chains.     

Characterization of blends of an amorphous polyamide with lightly sulfonated polystyrene ionomers

Improved compatibility of blends of polystyrene and an amorphous polyamide was achieved by lightly sulfonating the polystyrene. Hydrogen bonding between amide groups and either sulfonic acid or metal sulfonate groups lowered the interfacial tension between the two polymers, which led to a much finer dispersed phase size in blends involving the sulfonated polystyrene. At relatively high sulfonate to amide ratios, the two polymers formed a miscible blend. Improved mixing of the phases was verified by shifts in the glass transitions, and the specific interactions that occurred were characterized by Fourier transform infrared spectroscopy.     

Interfacial tension and phase behaviour characteristics of petroleum sulfonate/lignosulfonate mixtures

The interfacial tension and phase behaviour characteristics of mixed-surfactant formulations containing petroleum sulfonate and lignosulfonate were investigated. Low interfacial tensions between oil and aqueous surfactant solutions were found to be closely related to the occurrence of a third phase, and hence to the general phase behaviour of the surfactant system. Ultralow interfacial tensions (>0.01 mN/m), which are well known between oil and pure petroleum sulfonate solutions, could still be achieved when using mixtures of petroleum sulfonate containing lignosulfonate. It is considered that these findings will have important economic implications in the recovery of oil from partially depleted oil fields.     

A Sulfonozanamivir Analogue Has Potent Anti‐influenza Virus Activity

Influenza virus infection continues to cause significant, often severe, respiratory illness worldwide. A validated target for the development of anti‐influenza agents is the virus surface protein sialidase. In the current study, we have discovered a highly potent inhibitor of influenza virus sialidase, based on a novel sialosyl sulfonate template. The synthesised 3‐guanidino sialosyl α‐sulfonate, a sulfonozanamivir analogue, inhibits viral replication in vitro at the nanomolar level, comparable to that of the anti‐influenza drug zanamivir. Using protein X‐ray crystallography we show that the sialosyl α‐sulfonate template binds within the sialidase active site in a ¹C₄ chair conformation. The C1‐sulfonate moiety forms crucial and strong‐binding interactions with the active site's triarginyl cluster, while the 3‐guanidino moiety interacts significantly with conserved active site residues. This sulfonozanamivir analogue provides a new direction in anti‐influenza virus drug development.     

Reduction in domain size in polymer mixtures via charge transfer interactions

Blends of zinc neutralized sulfonated ethylene-propylene-diene elastomer (ZnS-EPDM) with poly(styrene-co-vinyl pyridine) have been compared with mixtures of the unfunctionalized rubber with the same copolymer. These binary component blends contain relatively low levels of interacting groups, which are, however, sufficient for the formation of intermolecular complexes. As a result of these interactions, marked enhancement in properties have been observed. In this study, small angle neutron scattering (SANS) is used to determine domain dimensions. The SANS experiments clearly show a decrease in domain size by three orders of magnitude when compatibilization via the sulfonate groups takes place. This reduction correlates with large changes in mechanical properties.     

Polystyrene Suspension Polymerization: The Effect of Polymerization Parameters on Particle Size and Distribution

Effects of polymerization parameters are studied to better understand interactions between parameters in stirred-tank polymerization reactors and to derive a regression model correlating polymer particle size and particle-size distribution with agitator speed, agitator diameter, tricalcium phosphate, dodecyl benzene sodium sulfonate concentrations, and mass cycle period. The derived equations give way to prediction of the polymerization conditions in order to obtain desired particle size and particle-size distributions which covers particle sizes between 0.3 and 5 mm. The roles of some other parameters and limiting agitation parameters are also investigated.     

水性聚氨酯用磺酸型扩链剂的制备与性能研究

以乙二胺与2-氯乙基磺酸钠为原料,优化合成条件为氢氧化钠调节反应液pH为10,2-氯乙基磺酸钠采用滴加的方式,以无水乙醇判断反应终点,合成了水性聚氨酯用磺酸型扩链剂N-(2-氨基乙基)-2-氨基乙磺酸钠。采用红外光谱、核磁氢谱、核磁碳谱、X射线衍射、元素分析等手段对产物进行了表征和结构分析,结果表明:以本文所述方法制得的产物提纯后纯度可达98.2%,作为亲水扩链剂可成功制备出高固含量低黏度的磺酸型水性聚氨酯分散液。     

High pressure liquid chromatography of alpha olefin sulfonates

Alpha olefin sulfonates (AOS) are a complex mixture of the posi-tional isomers of hydroxyalkane sulfonates, alkene sulfonates, and disulfonates. This paper describes a qualitative method for separat-ing these various components by reverse-phase high pressure liquid chromatography. The column utilized was a DuPont Zorbax TMS (4.6 mm × 25 cm) with a water/methanol (25:75, v/v) mobile phase containing sodium nitrate at a concentration of 0.4M. The hydroxyalkane sulfonate and alkene sulfonate peaks were identified using laboratory prepared standards. The disulfonate peaks were located using controlled sulfonation conditions. More work needs to be done to separate an overlap of C₁₆ 3-hydroxyalkane sulfonate and C₁₄ 2-alkene sulfonate in 1416 AOS. However, if studies are based on single carbon number AOS samples, the overlap of these peaks can be avoided. This method can be utilized as a qualitative tool for the comparison of sulfonation runs, the identification of AOS within a detergent, or the identfication of the olefin type used for sulfonation.     

Poly (acrylic acid) and poly (sodium styrenesulfonate) compatibility by Fourier transform infrared and differential scanning calorimetry

Blends of poly(acrylic acid) (PAA) and poly(sodium styrene sulfonate) (PSSNa) were prepared from polymer solutions by solvent evaporation. The observed decrease in PAA-solution pH upon addition of PSSNa suggests an inter-penetration of the two polymer chains, thus the polymer compatibility, in solution. The blend compatibility was studied with the attenuated total reflection-Fourier transform infrared (atr-FTIR) and the differential scanning calorimetry (DSC) techniques. The unique and composition-dependent glass transition temperature indicates that the two polymers are compatible, but the ΔT_g broadening suggests a certain degree of nano-heterogeneity. The T_g of pure PSSNa which was non-detectable in DSC, was calculated from the Fox equation. From FTIR data, the polymer compatibility could be attributed to the establishment of hydrogen bonds, and dipole-ion interactions between carboxylic groups, sulfonate groups, and sodium ion on the polymer segments.