Cross‐linked Copolyimide Membranes for the Separation of Gaseous and Liquid Mixtures

Cross‐linked polymer structures gain increasing attention as membrane materials because they can fullfill the demands for industrial applications. Thereby, not only good separation characteristics but also high temperature stability and chemical resistancy are required. Furthermore, it is important that the membrane materials be plasticization resistant, because it is found that this causes strong increasing permeability with a drastic loss in selectivity. Plasticization effects occur with polyimide membranes in the presence of high CO₂concentrations, hydrocarbons as propylene, propane, or aromatics. Unfortunately, these components are present in mixtures with high relevance being separated economically by membrane units or hybrid processes. In this article, the advantages of cross‐linked 6FDA (4,4′hexafluoro isopropylidene diphthalic acid anhydride)‐copolyimides are discussed based on experimental results for the separation of propylene/propane, benzene/cyclohexane, and high‐pressure CO₂/CH₄mixtures. Additionally, opportunities for implementing the membrane units in conventional separation processes are discussed.     

Ethyl Acrylate‐Hydroxyethyl Acrylate and Hydroxyethyl Acrylate‐Methacrylic Acid: Reactivity Ratio Estimation from Cross‐linked Polymer Using High Resolution Magic Angle Spinning Spectroscopy

Solution free radical copolymerizations of hydroxyethyl acrylate/methacrylic acid (HEA/MAA) and ethyl acrylate/hydroxyethyl acrylate (EA/HEA) have been conducted in m‐xylene (60 wt% solvent level) over the temperature range of 70–130°C using tert‐butyl peroxybenzoate as initiator. High resolution magic angle spinning spectroscopy (HR–MAS) and 2D–NMR have been utilized to characterize the copolymer gel for copolymer composition. The reactivity ratio values have been determined from low conversion copolymer composition data using the computer software package RREVM, which is based on the error in variables model (EVM) method. Also, Arrhenius‐type reactivity ratio expressions have been developed that describe how reactivity ratios vary with temperature.     

Cross‐metathesis of C‐Glycosides and Peptides

Peptides bearing an acryloyl residue at their N‐terminus were coupled with various C‐glycosides in an equimolar ratio via cross‐metathesis. The newly formed olefin was obtained with high E/Z selectivity in satisfying to high yields with low homodimerization of the starting materials. The posttranslational cross‐metathesis approach was shown to be suitable for the combinatorial synthesis of a small library of C‐glycopeptides.     

Thermo‐mechanical Properties of PEO‐PU/PAN Semi‐Interpenetrating Polymer Networks and their LiClO4 Salt‐Complexes

This paper is an investigation on the thermo‐mechanical properties of a new class of materials, which holds promise for its potential use as solid polymer electrolytes, i.e., SPE material. A series of poly(ethylene oxide)‐polyurethane/poly(acrylonitrile) (PEO‐PU/PAN) semi‐IPNs, along with their LiClO₄ salt complexes, were characterized for their thermal, mechanical and dimensional stability using DSC, TG‐DTA, UTM and DMTA. The glass transition temperature (T_g) of both the undoped and doped semi‐IPNs, obtained by DSC, remained well below room temperature (～?50°C to ?35°C), satisfying one of the essential requirements to serve as a SPE host matrix. The crystallization process in the PEO segments of the PEO‐PU/PAN semi‐IPNs was prevented at higher salt concentrations, which is attributed to the Li⁺ ion mediated pseudo‐crosslinks. Good thermal stability of the semi‐IPNs was evident from the degradation onset temperature (T₀～240°C) with a three‐stage degradation process, which is independent of the PAN content as observed from differential thermogravimetric studies. The incorporation of PAN in the PEO‐PU networks results in improved mechanical properties, such as tensile strength and modulus while retaining the flexibility of the semi‐IPNs. The peak temperatures and storage modulus obtained from DMTA correlates well with the observations of DSC and tensile measurements.     

Relationship Between the Polymer Structures and Destabilization of Polymer‐Containing Water‐in‐Oil Emulsions

The viscous properties, scanning electronic microscopy (SEM), and water/oil interfacial tension (IFT) of partially hydrolyzed polyacryamide (HPAM) and hydrophobically associating hydrolyzed polyacryamides modified with N‐dodecylacrylamide were studied with the objective of investigating the influence on destabilization of emulsions. As expected, the copolymers exhibit significant viscosity enhancing capacity and three‐dimensional network structures due to intermolecular hydrophobic associations, and also present high interfacial activities as the IFT decrease with increasing polymer concentration. As a result, the existences of copolymers increased both the viscosity of emulsions and the intensity of interfacial film, in which case slow down the diffusion of demulsifier molecules and enhance the stability of emulsions, finally, the separation of water from oil becomes more difficult.     

Mechanical Properties of Films from Hybrid Acrylic‐Polyurethane Polymer Colloids

A variety of polyurethane based on the polyaddition of isophoronediisocyanate and polypropyleneglycol has been used to prepare acrylic‐polyurethane hybrid polymer colloids, through either mini‐emulsion polymerization of their solutions in a mixture of monomers or seeded emulsion polymerization of this mixture from seeds of modified polyurethane containing dimethylolpropionic acid neutralized with triethylamine. The mixture of monomer is composed of 30% styrene, 30% methylmethacrylate, and 40% butylacrylate. The mechanical properies of films prepared through coalescence of these latexes where studied. The effect of various parameters such as the composition and the amount of polyurethane as well as the synthesis process are discussed.     

Photo‐oxidation and Stabilization of sPP and iPP/Boehmite‐Disperal Nanocomposites

Photo‐oxidation studies on polypropylene (PP)/organoclay nanocomposites were performed. Nanocomposites of isotactic (iPP) and syndiotactic (sPP) polypropylene were prepared by melt compounding. The nanofiller was Boehmite Disperal OS2–alumina hydrates (Al(OH)O) modified by C10–C13 alkylbenzene sulfonic acid. The nanofiller content was 1, 5, and 10 wt%. There is a clear pro‐degradation effect of filler for both types of polypropylene used. The extent of this effect depends on the amount of filler and type of polypropylene used. In the case of sPP samples, the pro‐degradation effect is proportional to the amount of filler in the whole concentration range of filler content used. In the case of iPP, there is a pro‐degradation plateau at 5 wt% content of filler and higher concentration of filler (10 wt%) does not increase the rate and the course of photo‐oxidation. Two long term stabilizers of HAS family were tested ‐ commercial oligomeric stabilizer Chimassorb 944 (CHIM) and synthesized combined HAS/phenol (TMP). Stabilizing efficiency depends on the filler content. CHIM is able to stabilize just the nanocomposites with the lowest content (1 wt%) of filler. There is no stabilizing effect of this HAS in the case of the higher amount of nanofiller (5 and 10 wt%) in both types of polypropylene. By contrast, the combined HAS/phenol‐TMP revealed some stabilizing efficiency over the whole range of filler content. The possible reasons for this difference are discussed. Interactions of filler with some HAS stabilizers were studied in cyclohexane as a model liquid for polypropylene by UV‐spectroscopy. Interaction resulted in the fixing of additive on filler. Much stronger interaction has been obtained for oligomeric CHIM in comparison with low molecular HAS.     

Synthesis,Characterization and Properties of Novel Amphiphilic Phosphated Ionomers by Ring‐Opening Reaction of Epoxidized Styrene‐Butadiene‐Styrene Triblock Polymer

A method for synthesis of novel phosphated ionomer of (styrene‐butadiene‐styrene) triblock polymer (SBS) from epoxidized SBS was developed. The optimum conditions for the ring‐opening reaction of the epoxidized SBS with aqueous solution of disodium hydrogen phosphate were studied. It was found that during the ring‐opening reaction phase transfer catalyst, ring‐opening catalyst and pH regulator were necessary to enhance the conversion of epoxy groups to ionic groups. The products were characterized with Fourier Transform Infrared Spectrophotometry (FTIR) and transmission electron microscopy (TEM). Some properties of the phosphated ionomer were studied. With increasing ionic groups or the ionic potential of the cation of the ionomer, the water absorbency emulsifying volume and the intrinsic viscosity of the ionomer increase, whereas the oil absorbency decreases. The ionomer possesses excellent emulsifying property, as compared with the sulfonated ionomer. The disodium phosphated ionomers in the presence of 10% zinc stearate showed better mechanical properties than the original epoxy SBS. Optimum mechanical properties occurred at the ionic group content of 0.95 mmol/g ionomer. When the ionomer was blended with crystalline polypropylene, a synergistic effect occurs with respect to the tensile strength. The ionomer behaves as a compatibilizer for blending equal amount of SBS and oil‐resistant chlorohydrin rubber (CHR) to form an oil resistant thermoplastic elastomer. SEM microphotographs indicated enhanced compatibility between the two components of the blend in the presence of the ionomer.     

Preparation and Characterization of Intercalated Polymethacrylamide/Na‐Montmorillonite Nanocomposites

Polymethacrylamide/Na‐montmorillonite nanocomposites have been prepared by free‐radical polymerization. All the nanocomposites were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, thermogravimetric analysis, and differential thermal analysis. The thermal properties of nanocomposites are notably improved by the presence of the montmorillonite layers in comparison with pure polymethacrylamide. X‐ray diffraction and scanning electron microscopy confirmed that polymethacrylamide could be easily inserted between the layers of Na‐montmorillonite to form intercalated nanocomposites, and significantly large d‐spacing expansions from 1.19 to 2.93 nm of the nanocomposites. Adsorptive properties of nanocomposites were also investigated.     

Electronic Properties and Morphology of Beam‐Oligomerized 3‐Hexylthiophene

Abstract

A novel means of lithographically forming fluorescent oligothiophene patterns is demonstrated. MgKα x‐ray and low energy electron irradiation of 3‐hexylthiophene (3HT) monomer condensed on a cold metal surface result in the formation of photoluminescent films as thick as several microns. The excitation maxima for the x‐ray‐ and electron‐formed samples are 350 and 405 nm, respectively, with corresponding emission maxima of 430 and 525 nm, indicating that the films are oligomeric rather than polymeric. Ultraviolet photoelectron spectra (UPS) of 3HT monomer and beam‐formed films have been compared with theoretically simulated density‐of‐states spectra of 3HT, thiophene, bithiophene, terthiophene, and quaterthiophene. The radiation‐induced changes in the 3HT UPS valence spectra are explained by delocalization of electrons along the oligomer backbone. Comparison of the experimental UPS and simulated spectra suggests that the average conjugation length of the beam‐formed films is less than six. This is consistent with the photoluminescence results. Fluorescence and atomic force microscopies of electron‐formed samples show the presence of oligomerized 3HT islands residing on a less fluorescent organic background. Electrical conductivity of the beam‐formed samples is low, on the order of 10^?9 cm^?1 ohm^?1, consistent with the formation of islands of conjugated material surrounded by a less electronically delocalized, insulating background. Lack of solubility of the beam‐formed films suggests that partial crosslinking and decomposition may also occur during the oligomerization process.     

Preparation and Catalytic Properties of Polymer Supported Dendritic Metal Complex

Polymer supported materials are extensively used as oxidizing agent, reducing agent catalysts, photosensitizers ion exchange resins and agriculturally and pharmacologically active agents1. The application of polymer metal complexes has been widely investigated2. The polymer supported complex undergoes swelling in a suitable solvent medium and provides enough surface area in carrying out electron transfer reactions, which clearly emphasizes the influence of a polymer network in heterogeneous ca…     

Structures and Mechanical Properties of PVC／Na^＋—Montmorillonite Nanocomposites

Poly(viyl chloride)/Na^ -montmorillonite(PVC/MMT)nanocomposites with different MMT contents were prepared via melt blending.Wide-angle X-ray diffraction(WAXD)and transmission electron microscopy(TEM)were used to characterize the structures.Effects of MMT content on the mechanical properties were also studied.It is found that PVC molecular chains can intercalate into the gallery of MMT layers during melt blending process,the stiffiness and toughness of the composites are inproved simultaneously within 0.5-7wt% MMT content,and the transparency and mechanical properties decrease as MMT conten further increases.     

Preparation and Characterization of trans‐1,4‐Polybutadiene Nanocomposites Containing in situ Generated Silica

Abstract

trans‐1,4‐Polybutadiene (tPBD) networks crosslinked free radically with dicumyl peroxide (DCP) were reinforced by in situ silica formed in a two‐step sol–gel technique. Changing the degree of crosslinking by changing the amount of DCP, or changing the amounts of the sol–gel components [tetraethoxysilane (TEOS) and dibutyltin diacetate (DBTDA)], changed the silica generated with regard to the amount precipitated, particle size, and degree of dispersion. Stress–strain measurements in continuous extension indicated good reinforcement, even at relatively low amounts of silica. Differential scanning calorimetry (DSC) indicated decreases in heat of crystallization with increases in the amounts of silica, but thermogravimetric analysis showed initial decomposition temperatures (IDT) remained relatively constant. Suggestions are made regarding interpretation of these properties in terms of the composite morphologies.     

Synthesis and Properties of Surfactants derived from N‐Acetyl‐D‐Glucosamine

The synthesis of 2‐acetamido‐2‐deoxy‐6‐O‐octanoyl‐D‐glucono‐1,5‐lactone 9 and 2‐acetamido‐2‐deoxy‐6‐O‐octanoyl‐α‐D‐glucopyranose 7 from 2‐acetamido‐2‐deoxy‐α‐D‐glucopyranose is reported. For both targets, the key intermediate was allyl 2‐acetamido‐3,4‐di‐O‐benzyl‐2‐deoxy‐6‐O‐octanoyl‐α‐D‐glucopyranoside 5. Surface tension measurements (critical micellar concentration of 22.3 mM and 5 mM for 9 and 7, respectively) showed up the surface activity of both compounds, while enzyme inhibition assays indicated that 9 could inhibit bovine β‐N‐acetylglucosaminidase (K_i=6.5 µM) but not Serratia marcescens chitobiase nor hen egg‐white lysozyme. Moreover, 7 was shown to induce chitinase production of S. marcescens and to be readily metabolized by these bacteria.      

Effect of Polymer and Surfactant‐Polymer Couples on the Acid-Catalyzed Hydrolysis of Phenyl Urea

The mechanism of the hydrolysis decomposition of phenyl urea in acid, polymer, and surfactant‐polymer media was investigated, the addition‐elimination mechanism with rate determining attack of water at N‐protonated substrate having already been studied. This study has introduced the polymer PEG (MW‐400) and (surfactant‐polymer) (ceteyl trimethyl ammonium bromide‐poly ethylene glycol) (CTAB‐PEG), (cetyl pyridinium bromide‐polyethylene glycol) (CPC‐PEG) (sodium dodecyl sulphate‐poly ethylene glycol) (SDS‐PEG), (Triton X‐100‐poly ethylene glycol) (TX‐100‐PEG), and (Brij35‐poly ethylene glycol) (Brij35‐PEG) in acid media. The results indicate that the presence of polymer and surfactant‐polymer enhances the rate of reaction at 80°C in the presence of 0.9 M H₂SO₄. Kinetic studies show that the reaction obeyed first‐order kinetics. The reaction kinetics can be well explained by micellar catalysis models like the PPIE.     

Preparation and Characterization of Polymer‐Protected Pt@Pt/Au Core‐Shell Nanoparticles

Poly(N‐vinyl‐2‐pyrolidone) protected Pt‐core bimetallic Pt/Au‐shell (Pt@Pt/Au) nanoparticles were prepared by multi‐step reduction of HAuCl₄ and H₂PtCl₆ alternately by hydrogen adsorbed on platinum atom. Transmission electronic microscopy (TEM) and x‐ray diffraction (XRD) were used to characterize Pt@Pt/Au nanoparticles. The structure of the shell of the nanoparticles seems to be the Au‐Pt solid solution.     

Preparation and Properties of Metal-Containing Nanocomposites Based on Isotactic Polypropylene and Butadiene–Acrylonitrile Rubber

Russian Journal of Applied Chemistry - The effect that nanofillers containing copper oxides stabilized with a maleinized low-density polyethylene matrix and prepared mechanochemically exert on the...     

Electrochemical Polymerization of Brilliant Cresyl Blue and Properties of the Polymer

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Synthesis,Structures, and Properties of Novel N‐Aryl‐phenanthren‐o‐iminoquinones

The interaction of 9,10‐phenanthrenquinone with primary amines has been studied. Use of sterically hindered anilines gave the phenanthren‐o‐iminoquinones in good yields. These compounds are structural analogues of o‐benzoquinones. Using single‐electron reduction, o‐iminoquinones may synthesize metal's free‐radical complexes.     

Preparation, Characterization and Magnetic Properties of PANI/La-substituted LiNi Ferrite Nanocomposites

Magnetic nanocomposites containing polyaniline （PANI）-coated La-substituted LiNi ferrite （LiNi0.5La0.02Fe1.98O4） were synthesized by in situ polymerization in aqueous solution of hydrochloric acid. The nanocomposites exhibited the magnetic hysteresis nature under applied magnetic field. The saturation magnetization （Ms） and coercivity （Hc） varied with the ferrite content. The obtained nanocomposites were characterized by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, scanning electron microscopy （SEM）, Fourier transform infrared spectroscopy （FT-IR）, UV-Visible spectroscopy and vibrating sample magnetometer （VSM）. TEM and SEM studies showed that the nanocomposites present the core-shell structure. The results of XRD patterns, FT-IR and UV-Visible spectra indicated the formation of PANI-LiNi0.5La0.002Fe1.98O4 nanocomposites and showed that the interaction existed between PANI backbone and ferrite particles in the nanocomposites. The bonding mechanism in the nanocomposites has been proposed.