Effect of electrolyte type on the electrokinetic behavior of sulfonated polystyrene model colloids

Sulfonated polystyrene latex particles were prepared by a two-stage shot-growth emulsion polymerization process in the absence of emulsifier. Sodium styrene sulfonate (NaSS) was used as an ionic co-monomer to produce a series of latex particles with the same particle size but with different surface charge densities. The electrophoretic mobility of this functionalized model colloid was studied in the presence of various types of inorganic electrolytes. The _e curves of these latexes exhibit a pronounced maximum at high electrolyte concentrations: 5·10^–2 M for 11 electrolytes and 10^–2 M for 21 and 12 electrolytes. When a 31 electrolyte (LaCl₃) was used, the electrophoretic mobility changed to positive values at high concentration due to the specific adsorption of lanthanum species. The experimental results for the electrokinetic characterization of these sulfonated polystyrene model colloids suggest that the surface of the particles is covered by a layer of oligomers or polymer chains which shift the shear plane toward the bulk solution, increasing the anomalous surface conductance of the polystyrene microsphere-electrolyte solution interface.     

Effect of electrolyte type on the electrokinetic behavior of carboxylated polystyrene model colloids

Carboxylated polystyrene latex particles were prepared by emulsifier-free emulsion polymerization of styrene using an azoinitiator (ACPA), which provides carboxyl end groups on the latex surface. Two latexes were characterized using TEM, PCS, conductimetric and potentiometric titrations, and electrophoretic mobility. To determine the hydrophobic or hydrophilic character of these latexes, the maximum adsorption of a nonionic surfactant (Triton X-100) was also studied and compared with other type of latexes. The electrophoretic mobility of these functionalized model colloids was studied in the presence of various types of inorganic electrolytes. The _e curves of these latexes exhibit a smooth maximum at an electrolyte concentration of around 10^–3 and 5·10^–3 M for 11, 21 and 12 electrolytes. When a 31 electrolyte (LaCl₃) was used, the electrophoretic mobility changed to positive values at high concentration due to the specific adsorption of lanthanum species. In general, the surface characteristics of these carboxylated latexes are very different in comparison to other latexes with the same functionality because the carboxyl groups are provided by the initiator, while in most of the cases these groups are provided by ionic comonomers (acrylic, methacrylic acids, etc.) used in the copolymerization with styrene.     

Polystyrene-ZnO core-shell microspheres and hollow ZnO structures synthesized with the sulfonated polystyrene templates

Mono-sized sulfonated polystyrene (PS) microspheres were used as templates to prepare PS-zinc oxide (ZnO) core-shell microspheres. Two different hollow ZnO structures were obtained after removing the PS cores by solvent extraction or calcinations. However, we obtained rod-like ZnO by either using unsulfonated PS microspheres as templates or without any templates. Transmission electron microscope (TEM) and scanning electron microscope (SEM) images were used to characterize the structures and morphologies of all the samples. X-ray diffraction (XRD), electron diffraction (ED) and infrared (IR) spectra were, respectively, used to study the crystal structure and composition of samples, respectively.     

Polymer blends of sPS/PA6 compatibilized by sulfonated syndiotactic polystyrene

Syndiotactic polystyrene (sPS) and polyamide-6 (PA6) are immiscible and incompatible and have been recognized. In this study, sulfonated syndiotactic polystyrene (SsPS-H) is employed as compatibilizer in the blend of sPS/PA6. During melt blending, the sulfonic acid groups of the SsPS-H can interact strongly with the amine end-groups of PA6 through acid-base interaction. In addition, SsPS-H is miscible with sPS when SsPS-H content is less than 20 wt.%. Therefore, the addition of SsPS-H to sPS/PA6 blends reduces the dispersed phase size and improves the adhesion between the phases. The glass transition temperatures of the PA6 component in the compatibilized blends shift progressively towards higher temperature with the content of SsPS-H-12 increase, indicating enhanced compatibility. On the other hand, the progressive lowering of the melting point and crystallization temperatures of PA6 in the blends with increasing SsPS-H contents compared to the incompatibilized blend, provide some insight into the level of interaction between the PA6 and SsPS-H. The compatibilized blends have significantly higher impact strength than the blends without SsPS-H. The best improvement in the impact strength of the blends was achieved with the content of the SsPS-H (11.9 mol%) about 5 wt.%.     

Preparation of highly sulfonated polystyrene model colloids

Previous attempts to prepare monodisperse styrene/sodium styrene sulfonate copolymer latexes by batch, seeded, and semicontinuous emulsion polymerization were unsuccessful at high concentrations of the functional comonomer. Broad, and sometimes bimodal, size distributions, and large amounts of water soluble homopolymer were obtained. After removal of free monomer, solute and adsorbed homopolymer and copolymer, the overall incorporation of the functional comonomer was found to be low. To overcome these problems, a two stage “shot-growth” or in situ seeding technique was developed. A first stage copolymerization was carried out with a low concentration of sodium styrene sulfonate: the purpose of the functional comonomer was to enhance the stability and regulate the size of the seed particles. When this reaction had reached high conversion (> 90%), a second stage monomer mixture was added. The ratio of styrene to sodium styrene sulfonate in this mixture determined the final surface charge density. The mechanism by which the NaSS is incorporated in the polymer particles is considered to be by solution copolymerization with solute styrene monomer to form surface active oligoradicals. These radicals adsorb on the particle surface, initiate polymerization and become inextricably bound, preventing their transfer back to the aqueous phase. By this means, it was possible to vary independently the particle size and surface charge density. High concentrations of functional comonomer could be polymerized without undue wastage (incorporations were only slightly less than 100%) or loss of monodispersity. In extreme cases, the area per functional group fell below the theoretical minimum, indicating considerable hydration of the surface layers.     

Thermal and hydrolytic stability of sulfonated polyimide membranes with varying chemical structure

Many important properties required for fuel cell applications including hydrolytic stability, depend on various factors like flexibility of the polymer backbone, ring structure and phase separation. This paper is primarily focused on studying the effect of the chemical backbone structure on the hydrolytic stability and other properties. To study the difference in the hydrolytic stability with change in the chemical backbone structure of sulfonated polyimides we synthesized phthalic sulfonated polyimides and naphthalenic sulfonated polyimides. Two series of phthalic sulfonated polyimides were prepared using 4,4′-oxydiphthalic anhydride (ODPA) and 4,4′-methylene dianiline (MDA), and 4,4′-(hexafluoroisopropylidine) diphthalic anhydride (6FDA) and oxydianiline (ODA). 4,4′-Diaminobiphenyl-2,2′-disulfonic acid (BDSA) was used to introduce sulfonic acid group into both series. Naphthalenic polyimides were synthesized from 1,4,5,8-naphthalenetetra-carboxylic dianhydride, BDSA, MDA and ODA. Also to observe other properties according to variation of sulfonic acid content, the degree of functionalisation was effectively controlled by altering the mole ratio between the sulfonated and non-sulfonated diamine monomers in phthalic sulfonated polyimides. The hydrolytic stability of the polyimides was followed by FT-IR spectroscopy at regular intervals. Polyimides prepared using naphthalenic dianhydride, NTDA, exhibited higher hydrolytic stability than the phthalic dianhydrides. The proton conductivity, ion exchange capacity (IEC) and water uptake measurements revealed the dependence on the molecular weight of the repeating unit. The proton conductivity of the sulfonated polyimides was found to vary with chemical backbone structure.     

Fluorescence and light-scattering studies on the formation of stable colloidal nanoparticles made of sodium sulfonated polystyrene ionomers

The lightly sulfonated polystyrene ionomer is only soluble in some organic solvents, such as toluene and tetrahydrofurnan (THF). The mixture of its organic solution with water normally leads to macroscopic phase separation, namely precipitation. In this study, using the steady-state fluorescence, the nonradiative energy transfer and dynamic laser light scattering, we demonstrate that the sulfonated polystyrene ionomers can form stable colloidal nanoparticles if the THF solution of the ionomers is dropwisely added into an excessive amount of water, or vice verse, water is added in a dropwise fashion into the dilute ionomer THF solution under ultrasonification or fast stirring. The hydrophobic core made of the polystyrene backbone chains is stabilized by the ionic groups on the particle surface. Such formed stable nanoparticles have a relatively narrow size distribution with an average diameter in the range of 5–12 nm, depending on the degree of sulfonation, the initial concentration of the ionomer THF solution, and the mixing order. This study shows another way to prepare surfactant-free polystyrene nanoparticles. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1593–1599, 1997     

Dynamic mechanical properties of sulfonated polystyrene/alumina composites

Amino units were grafted onto the surface of small particle size alumina by reaction with 3-aminopropyltriethoxysilane. Atactic polystyrene (PS) was sulfonated (1-14 mol% sulfonation) and mixed with both modified and unmodified alumina at filler loadings varying from 30 to 80 wt %. The resulting composites were characterized by differential scanning calorimetry, Fourier transform infra-red spectroscopy, and dynamic mechanical spectroscopy in the glass transition region at a frequency of 1 Hz. Whereas mixtures of unsulfonated PS with either filler showed essentially no change in T_g with filler content, sulfonated PS saw its T_g increase as a function of filler loading at a rate which was greater following modification of the alumina. At a fixed filler loading of 30 wt%, the composite rubbery plateau modulus was found to increase with copolymer sulfonic acid content, while the loss tangent maximum corresponding to the glass transition broadened and decreased. These observations were interpreted as a manifestation of the decrease in polymer mobility brought upon by the formation of noncovalent crosslinks resulting from the proton transfer from the sulfonic acid units on the polymer to hydroxyl and/or amino units at the surface of the filler. © 1994 John Wiley & Sons, Inc.     

Steric stabilization of polystyrene colloids using thiol-ended polyethylene oxide

Thiol-ended polyethylene oxide (I) has been prepared from the esterification of thioglycolic acid with monomethylether of polyoxyethylene glycol. Emulsion polymerization of styrene (and, in a few cases, methylmethacrylate as comonomer) was carried out in the presence of I using either water-soluble azo initiator or t-butylhydroperoxide. In the former case, bimodal particle size distribution was obtained while monodisperse latexes could be prepared in the latter case. Then a redox system was formed from I and t-BuOOH so that I was both an initiator and a transfer agent. Good steric stabilization of the latexes was observed. The polyethylene oxide sequence of I was partly incorporated at the surface of the latex particles, but the incorporation yield remained limited (between 7 and 18%). Most of the resdue of I remained in the serum.     

Amphoteric polystyrene latex colloids: polymerization pathway and the control of particle size and potential

Amphoteric polystyrene latex colloids were prepared by the emulsifier-free emulsion polymerization of styrene. Two co-monomers, methacrylic acid (MA) (anionic) and dimethyl aminoethyl methacrylate (DMAM) (cationic) were used to promote the amphoteric nature of the resultant surfaces. Parameters such as particle size and the isoelectric point (IEP) were measured as a function of polymerization recipe. Particle size decreased with increasing initiator concentration according to the equation: log [d _w]=–0.67 log [I] + 0.316 whered _w is the weight average particle diameter andI is the concentration of initiator (potassium persulphate).The particle size also decreased with increasing temperature, increasing pH and addition of surfactant. Particle size was unaffected by the methacrylic acid content. The isoelectric point pH was decreased on decreasing initiator concentration and on increasing methacrylic acid content.The polymerization pathway was deduced to involve the cationic DMAM during the initiation phase and to involve the anionic MA as well as styrene, during the growth stage. A full polymerization pathway involving the formation of oligomeric DMAM micelles was postulated.     

Selective surface modification of syndiotactic polystyrene films: A study by Fourier transform- and confocal-Raman spectroscopy

A helical crystalline modification of syndiotactic polystyrene (sPS), the δ-form, was employed to prepare solution-cast films selectively sulfonated on the surface. This result was achieved because of the unusual transport characteristics of the δ-form, exhibiting comparatively large diffusivity and solubility values for low-molecular weight compounds such as chloroform, which can be effectively used as a carrier solvent. The results of sulfonation of the δ-form are compared with those obtained with a trans-planar crystalline modification of sPS (β-form). The latter was found unsuitable for selective surface modification. The analysis of the sulfonated films was carried out by FT-Raman and confocal-Raman spectroscopy. The first technique was used to investigate the average composition of the samples in terms of sulfonation degree and crystalline structure. It also allowed us to construct calibration curves to be used in connection with the confocal-Raman data. The latter technique was employed to generate images with spectroscopic contrast and to quantitatively characterize the depth-profiles of the investigated films.     

The stability of semi-interpenetrating polymer networks based on sulfonated polyimide and poly(ethylene glycol) diacrylate for fuel cell applications

A series of the semi-interpenetrating polymer network (semi-IPN) membranes based on sulfonated polyimide and poly(ethylene glycol) diacrylate were prepared and characterized comparing with pure sulfonated polyimide membrane and commercially available membrane, Nafion^® 117. The proton conductivity increased with the increase of poly(ethylene glycol) diacrylate contents in spite of the decrease in ion exchange capacity which is a key factor to improve the proton conductivity. The water stability of semi-IPN membranes containing poly(ethylene glycol) diacrylate is higher than the pure sulfonated polyimide membrane. Morphological structure showed that amorphous nature of the films also increased with the poly(ethylene glycol) diacrylate contents, which could make a crosslink, so that the crystallinity of polyimide could disappear. Semi-IPN membranes based on sulfonated polyimide and poly(ethylene glycol) diacrylate, which show good conductivity comparable to Nafion^® 117 in the range of 20-50% content of poly(ethylene glycol) diacrylate, could be promising proton conducting membranes in fuel cell application.     

二氧化锆微球表面键合磺化交联聚苯乙烯固相萃取填料的制备及应用

以聚合诱导胶体凝聚法(PICA)制备二氧化锆微球,用钛酸酯偶联剂对其进行表面改性,使其接枝上碳碳双键基团。在溶液体系中,该双键与单体苯乙烯和二乙烯苯在自由基引发下交联聚合,形成的聚合物包覆在二氧化锆微球表面。再通过磺化方法将磺酸基离子连接到苯环上,得到阳离子交换固相萃取填料。通过红外光谱、扫描电镜/X射线能谱等手段对其进行了表征。将装填得到的固相萃取柱与高效液相色谱联用,测定了水中的甲基磺草酮、阿特拉津和乙草胺。3种化合物的色谱峰面积与质量浓度呈良好的线性关系,相关系数(r²)均大于0.99;甲基磺草酮、阿特拉津和乙草胺的检出限分别为5.41、6.72和13.4 μg/L。结果表明,制得的聚合物包覆二氧化锆微球的粒径为6~8 μm,用该填料制成的固相萃取小柱对3种目标物的吸附率高。     

Monodispersed Magnetic Polystyrene Beads with Excellent Colloidal Stability and Strong Magnetic Response

Monodispersed polystyrene beads incorporated with Fe₃O₄ nanoparticles are prepared via dispersion polymerization. The resultant magnetic beads present well‐defined composite structures, excellent colloidal stability, and strong magnetic response. The formation mechanism for the monodispersed composite beads, incorporated with preformed Fe₃O₄ nanocrystals, was investigated. The potential applications of the monodispersed magnetic beads in bacteria capturing were demonstrated. After being coated with anti‐Salmonella CSA‐1 antibody, the magnetic beads show capturing efficiencies of >99.4% in isolating Salmonella sp.

     

Mixture diffusion of sulfonated dyes into cellulose membrane. III. Application of parallel diffusion model to binary system of direct dyes with different affinity

Mixture diffusion of two dyes (C.I. Direct Blue 15 (DB15) and C.I. Direct Yellow 12 (DY12)) with different affinity onto the substrate into cellulose membrane from the binary solution was studied at 55°C. Uptake curves and concentration–distance profiles were measured experimentally in the ratios (DB15:DY12) 1:0.5, 1:1 and 1:2. It was examined whether the diffusion of the dyes could be analyzed based on the parallel diffusion theory of surface and pore diffusion. It was revealed that the diffusion of DB15 with higher affinity could be analyzed based on the model in the ratios 1:0.5 and 1:1, although the theoretical value deviated slightly from the data in the concentration–distance profile in the ratio 1:1. On the other hand, the diffusion of DY12 with smaller affinity could not be described by the model, because the diffusivity of the dye changed during the adsorption process against the assumption of the model.     

Miscible blends of zinc-neutralized sulfonated polystyrene and poly(2,6-dimethyl 1,4-phenylene oxide)

Zinc-neutralized sulfonated polystyrene ionomers (ZnSPS) and poly(2,6-dimethyl 1,4-phenylene oxide) homopolymer (PXE) form miscible blends up to at least 7.8 mol % sulfonation, as measured by thermal and mechanical criteria. The addition of an equal weight of PXE raises the glass transition temperature of ZnSPS by 40–50°C. However, this miscibility is not achieved by eradicating the microdomain structure present in ZnSPS, even though the PXE coils are considerably larger than the spacings between ionic aggregates. Small-angle x-ray scattering indicates that while the average interaggregate spacing is roughly the same in ZnSPS and its 50/50 blend with PXE at a given sulfonation level, the extent of phase separation is reduced upon PXE addition, indicating that more ionic groups are dispersed in the matrix. Factors influencing miscibility in the ZnSPS/PXE materials and related blends are discussed.     

Rheological and thermal studies of polystyrene calcium phosphate nanocomposites

Polystyrene‐calcium phosphate nanocomposites were prepared in an internal mixer by the melt mixing technique with as synthesized calcium phosphate nanoparticles. The composites were characterized by different techniques. Rheological aspects of the composites revealed the ease of processability and viscosity characteristics of the composites. Thermogravimetric analysis of the composites showed that the thermal stability of the composites improved by the incorporation of the nanofillers especially for the 3% and 5% filled systems. Flammability tests were carried out with a microcalorimeter, and it was found that the heat release rate decreased with respect to the filler loading.     

Improvement of the thermal stability of cluster‐crosslinked polystyrene and poly(methyl methacrylate) by optimization of the polymerization conditions

The polymerization conditions for polystyrene and poly(methyl methacrylate) crosslinked by 0.5 mol % of the cluster Zr₆O₄(OH)₄(methacrylate)₁₂ were optimized by applying a step polymerization procedure. The onset of thermal decomposition was thus increased up to about 50° for polystyrene and about 110° for poly(methyl methacrylate). The increase in thermal stability correlated with a higher char yield. The glass transition temperatures were also increased by about 15°. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6586–6591, 2005     

Synthesis and properties of polystyrene/polydimethylsiloxane graft copolymers

Polystyrene-graft-polydimethylsiloxane (PS-g-PDMS) copolymers with different PDMS content were synthesized by the radical bulk copolymerization of PDMS macromonomer and styrene. The copolymers were characterized by Fourier transform infrared (FT-IR), ¹H-nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), transmission electron microscopy (TEM) and the mechanical properties of the copolymers were also carried out. It was indicated that the notched impact strength and elongation at break of the polymers increased with the increase of PDMS content. The thermal stability of PS-g-PDMS is better than that of PS. __________ Translated from Journal of East China University of Science and Technology 2005, 31(2) (in Chinese)     

Heterogeneous ion-exchange membranes based on sulfonated poly(1,4-phenylene sulfide) and linear polyethylene: preparation, oxidation stability, methanol permeability and electrochemical properties

Poly(1,4-phenylene sulfide) was sulfonated with chlorosulfonic acid in 1,2-dichloroethane. The product (IEC = 2.38 mequiv./g) was ground and sieved (mesh size 63 μm) to obtain small particles. The particles and linear polyethylene were mixed in various ratios and the resulting blends were press-molded at 150 °C to obtain the membranes. Membranes containing up to 66 wt.% of sulfonated particles could be prepared without any problem in mechanical strength. The membranes were characterized by their stability in oxidative environment, ionic conductivity, and diffusive permeability to methanol. The membrane containing 66 wt.% of sulfonated particles was almost as conductive as Nafion 117; it exhibited, however, much lower diffusive permeability to methanol. In a strongly oxidative environment (3% aqueous H₂O₂ at 70 °C), the prepared membranes were less stable than Nafion 117, but much more stable than membranes with sulfonated poly(styrene-co-divinylbenzene) particles. In preliminary laboratory tests with H₂/O₂ and direct methanol fuel cells, the prepared membranes with high concentrations of sulfonated particles performed similarly to Nafion 117.