Comprehensive two-dimensional liquid chromatography of polymers

The need for and the emergence of comprehensive two-dimensional liquid chromatographic separations of synthetic polymers are reviewed in this paper. LC×SEC is shown to be a particularly valuable two-dimensional technique in this domain. An improved (symmetrical) configuration based on a single 10-way switching valve is described. The use of LC×SEC to understand and optimize one-dimensional separations is illustrated, as well as the potential of the technique for the separation and characterization of functional polymers and copolymers.     

Photo and electrically switchable behavior of azobenzene containing pendant bent‐core liquid crystalline polymers

New class of photo and electrically switchable azobenzene containing pendant bent‐core liquid crystalline monomers ( AZBM 1, 2 , and 3 ) and their polymers ( AZBP 1, 2 , and 3 ) are reported. The synthesized precursors, monomers, and polymers were characterized by FT‐IR, ¹H, and ¹³C NMR spectroscopy. Thermal stability of polymers was examined by thermogravimetric analysis and revealed stable up to 260 °C. The mesophase transition of monomers and polymers are observed through polarized optical microscopy (POM) and further confirmed by differential scanning calorimetry (DSC). The electrically switching property of monomers and their polymers were studied by electro‐optical method. Among the three monomers AZBM 1, 2 , and 3 , AZBM 1 and 2 exhibit antiferroelectric (AF) switching and AZBM 3 exhibits ferroelectric (F) switching behavior. On the other hand, low molecular weight polymers ( AZMP 1, 2 , and 3 ) show weak AF and F switching behavior. The photo‐switching properties of bent‐core azo polymers are investigated using UV‐vis spectroscopy, trans to cis isomerization occurs around 25 s for AZBP‐1 and 30 s for AZBP‐2 and 3 in chloroform, whereas reverse processes take place around 80 and 90 s. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Fast switching ferroelectric liquid-crystalline polymers

The principles of ferroelectricity, especially in liquid crystals (FLC) and polymers, are briefly presented. In a liquid-crystalline side chain polyacrylate electro-optical switching with response times of 200–400 μs was measured. Besides the ferroelectric switching an even shorter electroclinic switching process was detected. The influence of the spacer length and the molecular weight on the ferroelectric properties is discussed. The kind and number of chiral centers and their location in the side group strongly affects the electrooptical properties. In one polymer a change of the optical contrast caused by a sign reversal of the spontaneous polarization was found. In another FLC polymer three switching states (antiferroelectric behaviour) were detected. With coloured and fluorescent FLC polymers, obtained by mixing or by copolymerization new promising applications in electrooptical devices are expected.     

Metal filament growth in electrically conductive polymers for nonvolatile memory application

Solution processable polymers that can reproducibly form metal filament by applying voltage are investigated for nonvolatile memory application. Up to present, the understanding of materials enabling to make the metal filament has not been well-documented and the vacuum deposition methods were dominantly used in device fabrication. After screening various polymers, we found that only the polymers having two functionalities, the presence of strongly coordinating heteroatom (S or N) with metal ions and the electrical conductivity, showed the reproducible filament formation behavior. Among the polymers screened, the regiorandom poly(3-hexylthiophene) showed the best switching endurance over 30,000 write-read-erase-read cycles without any switching failure.     

Losses evaluation in converters using the calorimetric technique

In this paper, a measurement technique of losses in the switching cell, based on calorimetric technique is presented. A special calorimeter was designed to be able to access the heat generated by an operating converter. Power component losses are studied according to the cyclic ratio and to operating frequency and an extraction method of the different terms of these losses, using calorimetric measurements, is presented. An accurate expression of the switching losses in the power semiconductors devices is proposed.     

Characterization of polymers by multi-step thermal desorption/programmed pyrolysis gas chromatography using a high temperature PTV injector

Thermal treatment hyphenated with gas chromatography is a versatile and powerful tool in the study of polymer characterization. An inexpensive system where thermal treatment at different temperatures occurs inside a Programmable Temperature Vaporization injector (PTV) is described. The samples investigated, commercial plastics, are complex mixtures that contain several polymers and additives. These plastics as well as their pure constituents are subjected to multi-step thermal treatment. The individual chromatograms of the various constituents of the polymeric sample are correlated with those of the final material in order to identify additives (thermal desorption) and degradation products (pyrolysis). Results obtained with the new method indicate the interesting potentials of the technique for the characterization of polymer compositions. Reproducibility of absolute and relative peak areas has been considered and found to be acceptable. The absence of a heated transfer line and switching valves, which are always present in conventional set-ups, eliminates the risk of losses of high molecular weight components. Further advantages of the technique proposed are simplicity, versatility, and its inexpensive nature.     

A Mini Review: Electrospun Hierarchical Nanofibers

Electrospinning is a technique that allows the fabrication of continuous fibers with diameters down to a few nanometers. This technique provides a convenient and versatile method for preparing hierarchical nanofibers from a rich variety of materials that include almost all soluble or fusible polymers. The polymers can be chemically modified and can also be tailored with additives. The method provides access to entirely new materials. Until now, electrospinning is also widely being applied in laboratory and industry.     

Amphiphilic poly-n-vinyl-2-pyrrolidone: Synthesis,properties, nanoparticles

Water-soluble amphiphilic polymers based on N-vinyl-2-pyrrolidone (Amph-PVP) have been synthesized. Amphiphilic diblock polymers have been obtained via a single-step technique. For the synthesized amphiphilic polymers, the critical concentrations of mycelium formation (CCM) have been determined. The structure of the polymers obtained was confirmed by IR and NMR spectroscopy. The critical concentration of micelle formation (CCM) for the synthesized polymers has been found to be in the micromolar range. The fluorescent dye 1,1′-dioctadecyl-3,3,3′,3′-tetramethylindocarbocyanine perchlorate (Dil) was chosen as a model substance for the synthesis of nanoparticles. Micellar particles were obtained via an ultrasonic technique followed by evaporation of the organic solvent (emulsion method).     

Determination of trace metals in polymers by flameless atomic absorption with a solid sampling technique

A method for determining trace metals in polymers which combines flameless atomic absorption with a solid sampling technique is described. The method is applied to the analysis of iron, copper and chromium and is compared with results obtained from analysis of solutions of the polymers. Optimal conditions for achieving maximal accuracy and sensitivity are discussed. The effects of various matrix interferences and the heterogeneous distribution of trace metals in polymers are discussed.     

Low‐temperature side‐chain cleavage and decarboxylation of polythiophene esters by acid catalysis

Solubility switching of polymers is very useful in thin layer processing of conjugated polymers, as it allows for multilayer processing and increases the stability of the polymer. Acid catalyzed thermocleavage of ester groups from thiophene polymers carrying primary, secondary, and tertiary substituents have been examined by TGA‐MS using different sulphonic acids. A substantial lowering of the cleavage temperature is observed, and the ester cleavage can even be performed in situ on roll‐to‐roll‐coated films on polyethylene terephthalate (PET). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Thermal desorption characterisation of molecularly imprinted polymers. Part I: a novel study using direct-probe GC-MS analysis

A novel thermal desorption technique using a direct-probe device (Chromatoprobe) attached to a gas chromatograph–mass spectrometer is presented for the thermal pretreatment, characterisation and analysis of molecularly imprinted polymers. The technique is demonstrated as effective for the removal of volatile materials, including template and unreacted monomers, from methacrylic acid–ethylene glycol dimethacrylate copolymers imprinted with 2-aminopyridine. Mass spectrometry is a powerful technique for polymer bleed characterisation. Thermal desorption studies on reloaded template and related compounds are reported as a means of assessing polymer morphology, specific binding by imprinted polymers compared with reference non-imprinted polymers and selective binding by an imprinted polymer for its template. Calibration studies on the thermal desorption technique using an internal standard are presented with R ² > 0.999. The technique provides a novel method for assessment of polymer thermal stability, composition and morphology.     

Mass spectrometric analysis of halogenated polymers

Controlled pyrolysis—electron impact mass spectrometry is a general method for the identification of polymers. It is shown here to be useful for the diagnosis of commercial halogen-containing polymers. The application of the technique both in a purely fingerprinting role, and by rationalising spectra in terms of structure and generalised thermal degradation pathways, is demonstrated. Inorganic oxides can have a secondary effect on degradative behaviour and spectral form.     

Polymers for electrical and optical data storage

Polymers possess great significance in data storage technology. Taking as an example electrical and optical data storage, the state of development, properties required and opportunities for application of selected polymers are discussed, namely: (i) ferroelectric polymers with low switching voltages and extremely short switching times for electric data storage; and (ii) transparent polymers with low birefringence and high thermal stability for optical data storage. In the area of electrical data storage devices/memories, ferroelectric polymers have not been able to establish themselves up to now due to their long switching time and limited thermal stability. However, recent investigations show that suitable copolymers based on PVDF/TrFE copolymers in ultra-thin layers can achieve switching times of ≤100 ns. Nevertheless, the limited thermal stability of PVDF/TrFE copolymers prevent them from being integrated into the usual manufacturing process for Si-based data storage devices (D-RAM resp. S-RAM) and thereby frustrates the desired objective of producing nonvolatile random access memories (NV-RAMs). In the area of optical data storage technology, polycarbonate (PC) has established itself due to its favorable combination of properties. Thus, audio compact disks (CDs) are manufactured exclusively of PC, while high-flow PC types of high optical purity are clearly the preferred substrate material for optical data storage disks. The increasingly stringent requirements to be met in terms of lower birefringence and better thermal stability mean that the development of suitable modified or substituted polycarbonates is required. The development work being carried out worldwide in this area is reviewed here, and new suitable substituted polycarbonates with lower birefringence and significantly increased thermal stability up to glass temperatures of 238°C are presented. In addition, we deduce structure—property relationships for the above-mentioned structurally modified polycarbonates, specifically considering rotation potentials along the polymer backbone.     

Characterization of Electroinitiated and Radiation Polymerized Poly(Butadiene Sulfone)

Polymerization of butadiene sulfone was accomplished by using two different methods. The first method involves electrochemical polymerization of the monomer using the constant potential electrolysis technique. Oxidation of the monomer under nitrogen atmosphere in an acetonitrile-tetrabutylammonium tetrafluoroborate system yields brown, tarry polymers. On the other hand, the second initiation method, which was radiation polymerization, yields white, powdery polymers. Structural analyses of the two polymers by various spectroscopic methods suggest a structure consisting of two different units in different proportions.     

偶氮型液晶高分子的研究及应用

偶氮液晶高分子由于其具有特殊的光致异构和光致变色等光学性质,在光信息贮存材料、光开关材料和非线性光学设备材料等领域具有巨大的应用潜力,近年来得到了国内外研究者的广泛关注。本文概述了偶氮型液晶高分子的结构特征,详细介绍了主链型偶氮液晶高分子、侧链型偶氮液晶高分子、树枝状偶氮液晶高分子以及星型偶氮液晶高分子的研究现状及在光储存、光开关及光调制偏振片等方面的应用进展,指出了存在的问题和研究方向。     

Thienylmethylene Oxindole Based Conjugated Polymers via Direct Arylation Polymerization and Their Electrochromic Properties

Direct arylation methods have been used to polymerize thienylmethylene oxindoles(TEIs) and 3,3-bis[[(2-ethylhexyl)oxy]methyl]-3,4-dihydro-2 H-thieno-[3,4-b][1,4]dioxepin(ProDOT) for new donor-acceptor conjugated polymers. The polymers exhibited blue hues in neutralstate with distinct color-to-transmissive reversible electrochromic switching under applied potentials from 0 V to +1.5 V, and showed high coloration efficiencies(436-438 cm~2·C~(-1)) in near-infrared regions with high switching speeds around 1-2 s under ambient conditions.     

Banana-shaped side chain liquid crystalline siloxanes

Eight banana-shaped side chain liquid crystalline oligomers and polymers have been synthesized by hydrosilylation of vinyl-terminated bent-core mesogens with trimethylsilyl-terminated siloxanes. The synthesized oligomers and polymers, and their olefinic precursors, were investigated by polarizing optical microscopy (POM), differential scanning calorimetry, X-ray diffraction (XRD), electro-optical experiments and Maldi-Tof. The short-tailed olefins form a Col_r mesophase, whereas those with longer chains exhibit the SmCP_A mesophase. All the oligomers and polymers studied show liquid crystalline properties and do not crystallize upon cooling. Most oligomers with around four repeating siloxane units, show a lamellar (layer) structure and antiferroelectric switching properties, the SmCP_A phase. XRD shows that the layer spacings are hardly influenced by the length of the terminal tails. The oligomer prepared from the smallest olefinic precursor, having the shortest alkyl tail, shows an XRD pattern reminiscent of a columnar phase, although POM displays domains of opposite chirality, and no switching behaviour could be detected. The polymers with around 35 repeating siloxane units are liquid crystalline, but due to their high viscosity a thorough characterization of the liquid crystalline phases was impossible.     

Blend Composites Based on Polystyrene–CdSe Quantum Dots and Polystyrene–Gold Nanoparticles Hybrid Systems

Polystyrenes of different molecular masses are synthesized by controlled radical polymerization via the reversible addition fragmentation chain transfer mechanism. The resulting polymers are used for designing nanocomposites based on cadmium selenide quantum dots and gold nanoparticles. It is demonstrated that the photoluminescence of quantum dots in the sol grows appreciably during continuous irradiation for 5–6 h but is reduced during the “light switching off–switching on” process. It is shown that, upon the addition of gold nanoparticles, the photoluminescence of quantum dots in the sols changes insignificantly.     

Universal technique for studying electron transport in polymers

A universal technique was developed for studying electron transport in polymers, which consists in the combination of the time-of-flight technique in the surface and bulk carrier generation modes with measurement of transient radiation-induced conductivity. Central to the technique in question is the time-of-flight method with homogeneous irradiation. The procedure was implemented on the basis of an ELA-50 electron beam device with variable electron energy (3–50 keV). The practicability of the universal technique was demonstrated using the model polymers polyvinylcarbazole and molecularly doped polycarbonate as examples.     

基于高真空实验技术活性阴离子聚合方法学研究进展

活性阴离子聚合能够得到分子量及分布可控的模板聚合物,是环状、树枝状以及多臂星形等复杂拓扑结构聚合物的重要合成方法。高真空实验技术能够使反应环境彻底封闭、杜绝杂质影响从而得到更加精确的实验数据,因此成为活性阴离子聚合理论研究的重要手段。本文对基于高真空实验技术的活性阴离子聚合方法学研究进行了总结,通过多官能引发剂、“大单...