Sterically stabilized emulsion polymerization of styrene: Pseudo‐semicontinuous approach

The sterically stabilized emulsion polymerization of styrene initiated by a water‐soluble initiator at different temperatures has been investigated. The rate of polymerization (R_p) versus conversion curve shows the two non‐stationary‐rate intervals typical for the polymerization proceeding under non‐stationary‐state conditions. The shape of the R_p versus conversion curve results from two opposite effects—the increased number of particles and the decreased monomer concentration at reaction loci as the polymerization advances. At elevated temperatures the monomer emulsion equilibrates to a two‐phase or three‐phase system. The upper phase is transparent (monomer), and the lower one is blue colored, typical for microemulsion. After stirring such a multiphase system and initiation of polymerization, the initial coarse polymer emulsion was formed. The average size of monomer/polymer particles strongly decreased up to about 40% conversion and then leveled off. The initial large particles are assumed to be highly monomer‐swollen particles formed by the heteroagglomeration of unstable polymer particles and monomer droplets. The size of the “highly monomer” swollen particles continuously decreases with conversion, and they merge with the growing particles at about 40–50% conversion. The monomer droplets and/or large highly monomer‐swollen polymer particles also serve as a reservoir of monomer and emulsifier. The continuous release of nonionic (hydrophobic) emulsifier from the monomer phase increases the colloidal stability of primary particles and the number of polymer particles, that is, the particle nucleation is shifted to the higher conversion region. Variations of the square and cube of the mean droplet radius with aging time indicate that neither the coalescence nor the Ostwald ripening is the main driving force for the droplet instability. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 804–820, 2003     

Microemulsion polymerization of styrene in the presence of a cationic emulsifier

The principal subject discussed in the current paper is the radical polymerization of styrene in the three- and four component microemulsions stabilized by a cationic emulsifier. Polymerization in the o/w microemulsion is a new polymerization technique which allows to prepare the polymer latexes with the very high particle interface area and narrow particle size distribution. Polymers formed are very large with a very broad molecular weight distribution. In emulsion and microemulsion polymerizations, the reaction takes place in a large number of isolated loci dispersed in the continuous aqueous phase. However, in spite of the similarities between emulsion and microemulsion polymerization, there are large differences caused by the much larger amount of emulsifier in the latter process. In the emulsion polymerization there are three rate intervals. In the microemulsion polymerization only two reaction rate intervals are commonly detected: first, the polymerization rate increases rapidly with the reaction time and then decreases steadily. Essential features of microemulsion polymerization are as follows: (1) polymerization proceeds under non-stationary state conditions; (2) size and particle concentration increases throughout the course of polymerization; (3) chain-transfer to monomer/exit of transferred monomeric radical/radical re-entry events are operative; and (4) molecular weight is independent of conversion and distribution of resulting polymer is very broad. The number of microdroplets or monomer-starved micelles at higher conversion is high and they persist throughout the reaction. The high emulsifier/water ratio ensures that the emulsifier is undissociated and can penetrate into the microdroplets. The presence of a large amount of emulsifier strongly influences the reaction kinetics and the particle nucleation. The mixed mode particle nucleation is assumed to govern the polymerization process. At low emulsifier concentration the micellar nucleation is dominant while at a high emulsifier concentration the interaction-like homogeneous nucleation is operative. Furthermore, the paper is focused on the initiation and nucleation mechanisms, location of initiation locus, and growth and deactivation of latex particles. Furthermore, the relationship between kinetic and molecular weight parameters of the microemulsion polymerization process and colloidal (water/particle interface) parameters is discussed. In particular, we follow the effect of initiator and emulsifier type and concentration on the polymerization process. Besides, the effects of monomer concentration and additives are also evaluated.     

Synthesis of enantiomerically pure (purin-6-yl)phenylalanines and their nucleosides, a novel type of purine-amino acid conjugates

[Chemical reaction: See text] Enantiomerically or diastereomerically pure 4-(purin-6-yl)phenylalanines, a novel type of stable amino acid-purine conjugates, were synthesized by palladium-catalyzed cross-coupling reactions of protected 4-boronophenylalanines or 4-(trimethylstanyl)phenylalanines with diverse 6-halopurines (9-benzyl-6-halopurines and 9-(tetrahydropyran-2-yl)-6-halopurines as well as acyl- and silyl-protected 6-halopurine ribonucleosides and 2-deoxyribonucleosides). Free purine bases and nucleosides bearing (S)- or (R)-phenylalanine in position 6 were obtained after complete deprotection of the products of cross-coupling reactions. Reactivity trends for both of these cross-coupling and deprotection protocols have been compared in terms of practicability, efficiency, and stereoselectivity.     

Sterically and electrosterically stabilized emulsion polymerization. Kinetics and preparation

The principal subject discussed in the current paper is the radical polymerization in the aqueous emulsions of unsaturated monomers (styrene, alkyl (meth)acrylates, etc.) stabilized by non-ionic and ionic/non-ionic emulsifiers. The sterically and electrosterically stabilized emulsion polymerization is a classical method which allows to prepare polymer lattices with large particles and a narrow particle size distribution. In spite of the similarities between electrostatically and sterically stabilized emulsion polymerizations, there are large differences in the polymerization rate, particle size and nucleation mode due to varying solubility of emulsifiers in oil and water phases, micelle sizes and thickness of the interfacial layer at the particle surface. The well-known Smith-Ewart theory mostly applicable for ionic emulsifier, predicts that the number of particles nucleated is proportional to the concentration of emulsifier up to 0.6. The thin interfacial layer at the particle surface, the large surface area of relatively small polymer particles and high stability of small particles lead to rapid polymerization. In the sterically stabilized emulsion polymerization the reaction order is significantly above 0.6. This was ascribed to limited flocculation of polymer particles at low concentration of emulsifier, due to preferential location of emulsifier in the monomer phase. Polymerization in the large particles deviates from the zero-one approach but the pseudo-bulk kinetics can be operative. The thick interfacial layer can act as a barrier for entering radicals due to which the radical entry efficiency and also the rate of polymerization are depressed. The high oil-solubility of non-ionic emulsifier decreases the initial micellar amount of emulsifier available for particle nucleation, which induces non-stationary state polymerization. The continuous release of emulsifier from the monomer phase and dismantling of the non-micellar aggregates maintained a high level of free emulsifier for additional nucleation. In the mixed ionic/non-ionic emulsifiers, the released non-ionic emulsifier can displace the ionic emulsifier at the particle surface, which then takes part in additional nucleation. The non-stationary state polymerization can be induced by the addition of a small amount of ionic emulsifier or the incorporation of ionic groups onto the particle surface. Considering the ionic sites as no-adsorption sites, the equilibrium adsorption layer can be thought of as consisting of a uniform coverage with holes. The de-organization of the interfacial layer can be increased by interparticle interaction via extended PEO chains--a bridging flocculation mechanism. The low overall activation energy for the sterically stabilized emulsion polymerization resulted from a decreased barrier for entering radicals at high temperature and increased particle flocculation.     

On acrylonitrile polymerization in the presence of zinc salts

Acrylonitrile polymerization photoinitiated at 365 nm by pyrene and/or azobisisobutyronitrile in the presence of zinc salts in N,N-dimethylformamide solution has been studied by the rotating sector method. It was found that the ratio of the rate constants for propagation and termination (k_p/k_t) increases on addition of zinc salts (chloride, nitrate, acetate). This increase was more pronounced for the azobisisobutyronitrile photoinitiated polymerization of acrylonitrile then for its pyrene photoinitiated polymerization. The results confirm the previously expressed view concerning the dual role of zinc chloride in initiation as well as in propagation steps of acrylonitrile polymerization photoinitiated by aromatic hydrocarbons.

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Characterization of the patina formed on a low tin bronze exposed to aqueous hydrogen sulfide

The dark gray corrosion layer (patina) formed on the surface of a polished low tin bronze alloy following exposure to a deoxygenated and saturated aqueous solutions of H₂S has been characterized by X‐ray photoelectron spectroscopy, scanning electron microscopy‐energy dispersive spectroscopy and X‐ray diffraction. The system represents a model for bronze corrosion in reducing conditions where sulfate‐reducing bacteria in soils or deoxygenated seawater may generate H₂S during respiration. The initial surface was dominated by metallic copper together with Sn, Pb and Zn oxides and hydroxides. Surface enrichment of Pb and Zn was noted because of a smearing effect during polishing. At least some of the lead was crystalline. In contrast, the corrosion layer formed by H₂S(aq) exposure was dominated by polycrystalline Cu₂S (low and high chalcocite) and smaller concentrations of CuSO₄ · nH₂O. This surface was enriched with Zn as Zn(OH)₂. Lead was present as redeposited PbS (galena) crystallites in at least two different morphologies. Unlike bronzes exposed to oxidizing conditions, which develop protective SnO₂ layers, the H₂S(aq)‐exposed surface was considerably depleted in Sn. Copyright © 2014 John Wiley & Sons, Ltd.     

Simultaneous Quantification of Neomycin and Bacitracin by LC-ELSD

The first simultaneous quantification of neomycin and bacitracin using liquid chromatography evaporative light scattering detection as an alternative to MS detection and pre-/post-column derivatisation, respectively, was the aim of this study. The developed method was validated for two strength of neomycin and one strength of bacitracin in sterile pharmaceutical formulation and is a fast and efficient tool for content uniformity tests in quality control. With this method the separation of neomycin from sulfate and the base line separation of the four major components of bacitracin (bacitracin A, B1, B2 and B3) was achieved. These four components are responsible for 96% of the microbiological activity. A Phenomenex Synergi POLAR analytical column (250 mm × 4.6 mm, 4 μm I.D.) in combination with 0.5% perfluoropropionic acid and acetonitrile in gradient mode, the peaks of interest could be separated with high efficiency within 14 min. The calibration was performed using a second order regression with an R ² = 0.9999 for neomycin (B and C) sulfate and R ² = 0.9996 for bacitracin A, B1, B2 and B3. The results of the accuracy evaluation were 99.2 and 99.7%, respectively, for neomycin and 100.8% for bacitracin. Injection precision results are 0.4–1.5 RSD% recorded for six injections. The established method has a high potential for routine high-throughput analyses in the pharmaceutical industry.     

Comparative Studies of Er3☎ Ions in LiNbO3 Waveguides Produced by Different Methods

We compare the optical properties of Er^3? in LiNbO₃ waveguides produced by different techniques and find by confocal luminescence microscopy characteristic differences in the excitation and emission transitions. Besides a small redistribution among the regular defect sites, essentially no direct Er^3?—Ti^4? interaction can be observed in Ti^4? diffused waveguides. However a significant shift in transition energies is found, which increases with Ti^4?concentration. Based on earlier results we associate this shift with a decrease in the intrinsic electric field. In addition to a similar shift, we find in Zn^2? diffused waveguides new defect types which suggest a change in direct environment. Finally, in annealed proton exchange waveguides we find no interaction effects at all.     

Femtosecond multicolor transient absorption spectroscopy of colloidal silver nanoparticles

Time-resolved femtosecond multicolor absorption spectroscopy of silver nanoparticle (NP) colloids with particle diameter in range of 10–30 nm is presented. The amplified femtosecond excitation of the surface plasmon resonance band resulted in transient absorption spectra reflecting the electron-phonon relaxation dynamics, which takes place on the early picosecond time scale. The monitored band with enhanced absorption in the 490–540 nm spectral range exhibited red-shift with increasing pump fluency from 0.4 mJ/cm² to the 1.5 mJ/cm² level. The growth of the relaxation time with increasing pump fluency reveals the temperature dependent relaxation dynamics caused by the nanometer sized electron confinement in the case of silver. This effect was confirmed also by identification of the relaxation time dependence on the particle diameter at constant pump fluency. The complex experimental results revealed nonlinearities both in the laser excitation and electron relaxation processes.     

Photoinitiation. III. Polymerization of acrylonitrile photoinitiated by benzophenone in the presence of naphthalene

The polymerization of acrylonitrile photoinitiated by radiation of wavelengths 313 and 365 nm in the presence of benzophenone and naphthalene was studied. If radiation of wavelength λ = 313 nm which is absorbed by naphthalene as well as by benzophenone is used, a decrease of the acrylonitrile polymerization rate and of the molecular weight of the polymer is observed in comparison with the polymerization taking place in the absence of benzophenone. If a radiation of wavelength (λ = 365 nm) at which only benzophenone is excited is used, addition of naphthalene to the system acrylonitrile–benzophenone enhances the polymerization rate. The reaction mechanism which accounts for the observed behavior of the acrylonitrile polymerization is discussed.