Influence of the seed polymer on the chromatographic properties of size monodisperse polymeric separation media prepared by a multi-step swelling and polymerization method

Monodisperse polymer particle-based separation media were prepared by a multi-step swelling and polymerization method with two pairs of monomers and two porogenic solvents. Their chromatographic properties were compared to those of beads prepared by a corresponding suspension polymerization method without the use of seed polymer to ascertain the influence of the seed polymer on their porous structures. A large change in porous structure was observed when the swollen particle consisting of monomers and porogenic solvents contained at least one good solvent for the polystyrene seed polymer, allowing it to remain in the polymerizing medium. In contrast, when the polystyrene seed particle was excluded from the swollen oil droplets, due to its poor solubility in the monomers and the porogenic solvents, there was no difference in the chromatographic properties such as pore volume, pore size, pore size distribution, or retention selectivity between the multi-step swelling and polymerization method and the suspension polymerization method. Since the only difference between the multi-step swelling and polymerization method and the suspension method is the use of the seed polymer, it appears that a very small amount (< 1% v/v) of seed polymers in the enlarged swollen droplets plays an important role as a porogen and affects the porous structure as well as the chromatographic properties of the monodisperse polymer particle-based separation media. © 1993 John Wiley & Sons, Inc.     

Rodlike/flexible polyimide composite films prepared from soluble poly(amic diethyl ester) precursors: Miscibility,structure, and properties

Homogeneous precursor/precursor solutions with various compositions were obtained with appreciably high solid contents in N-methyl-2-pyrrolidone from soluble poly(amic diethyl ester) precursors of rodlike poly(p-phenylene biphenyltetracarboximide) (BPDA-PDA) and flexible poly(4,4′-oxydiphenylene biphenyltetracarboximide) (BPDA-ODA), which are hydrolytically more stable as well as more soluble than the corresponding poly(amic acid)s being equilibrated with the constituent monomers. Both optical microscopic and light scattering measurements showed that the dried precursor blend films and resultant polyimide composite films were optically transparent, regardless of compositions and process conditions. The composite films showed a single T_g behavior. However, for the composite of 30 wt % BPDA-PDA dispersed in the matrix of 70 wt % BPDA-ODA, a smectic crystalline-like aggregation of the BPDA-PDA component was detected on wide-angle x-ray diffraction patterns, indicative of microscopic phase separation between the two components. This phase separation was not detected on the optical microscopy, light scattering, and dynamic mechanical thermal analysis because of their resolution limits: Optical microscopy has a resolution of submicrometers, whereas dynamic mechanical thermal analysis and light scattering have a resolution of ca. 50 Å. Therefore, it is speculated that in the composite films BPDA-PDA and BPDA-ODA polyimide molecules have demixed on the scale of a few nanometers. The mean long periodicity, which was estimated from the small-angle x-ray scattering pattern, varied from 134 to 170 Å as the content of BPDA-ODA component increased. In addition, mechanical properties of the composite films were characterized. ©1995 John Wiley & Sons, Inc.     

Hyperbranched polyurethane as novel solid-solid phase change material for thermal energy storage

A series of novel hyperbranched polyurethane copolymer (HB-PUPCM) using hyperbranched polyester as chain extender was prepared via a two-step process. The phase transition behaviors and morphology of the HB-PUPCM films were investigated using differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMA), thermo-gravimetric analysis (TGA), wide-angle X-ray diffraction (WAXD), polarizing optical microscopy (POM) and tapping-mode atomic force microscopy (AFM). HB-PUPCM was proven to a good polymeric solid-solid phase change heat storage material.     

Review of proton conductors for hydrogen separation

There is a global push to develop a range of hydrogen technologies for timely adoption of the hydrogen economy. This is critical in view of the depleting oil reserves and looming transport fuel shortage, global warming, and increasing pollution. Molecular hydrogen (H₂) can be generated by a number of renewable and fossil-fuel-based resources. However, given the high cost of H₂ generation by renewable energy at this stage, fossil or carbon fuels are likely to meet the short- to medium-term demand for hydrogen. In view of this, effective technologies are required for the separation of H₂ from a gas feed (by-products of coal or bio-mass gasification plants, or gases from fossil fuel partial oxidation or reforming) consisting mainly of H₂ and CO₂ with small quantities of other gases such as CH₄, CO, H₂O, and traces of sulphur compounds. Several technologies are under development for hydrogen separation. One such technology is based on ion transport membranes, which conduct protons or both protons and electrons. Although these materials have been considered for other applications, such as gas sensors, fuel cells and water electrolysis, the interest in their use as gas separation membranes has developed only recently. In this paper, various classes of proton-conducting materials have been reviewed with specific emphasis on their potential use as H₂ separation membranes in the industrial processes of coal gasification, natural gas reforming, methanol reforming and the water–gas shift (WGS) reaction. Key material requirements for their use in these applications have been discussed.     

Production of oxy-rich air by RPSA for combustion use

The capital and energy costs of production of oxygen enriched air by a rapid pressure swing adsorption (RPSA) process can be reduced by decoupling the air drying and the air separation duties of the process. Integration of the oxygen-RPSA process with an enhanced combustion application system allows thermal swing adsorption drying of air feed to the RPSA process. The air separation process then can be run using an ad(de)sorption pressure envelope of 2:1 atmospheres, which significantly reduces the cost and energy of operation of the air compressor.     

Chromogenic polymer gels for reversible transparency and color control with temperature at a constant volume

The preparation and characterization of novel chromogenic materials has developed extremely rapid in the last years. Among them, thermotropic and thermochromic polymer gel networks have met with growing interest, because of their advanced properties. These novel polymer gels exhibit pronounced changes in transparency and/or color intensity in a practically relevant temperature range. For many future technical applications it is an essential condition, that the volume of the used gel materials is independent of temperature. A current overview of this field is given. Copyright © 2002 John Wiley & Sons, Ltd.     

Surface properties and aggregation of basic aluminium sulphate hydrolysis products: 1. Electrokinetic potential and hydration of BAS hydrolysis product particles

The action of pre-hydrolysed coagulants such as basic aluminium chloride (BAC) and sulphate (BAS) in water treatment is of considerable practical and fundamental interest. Variables such as working solution concentration, dosage, pH and ionic strength are known to be important. We have investigated the influence of these variables on the ζ-potential and degree of hydration of hydrolysis products of basic aluminium sulphate samples with different basicities. The products were characterised by a timed ferron complexation procedure, giving information on the degree of polymerisation of the BAS samples. Electrokinetic measurements showed that the ζ-potentials of hydrolysis product particles were consistently higher (more positive) for the higher basicity samples. The ζ-potential decreased with increasing concentration of the working solution and with increased dosage.

The degree of hydration of the hydrolysis products was investigated using the spin-lattice relaxation time of protons of water molecules bound to their surfaces. This was found to decrease with increasing basicity of BAS, indicating a greater degree of hydration. Since this effect is expected to decrease ζ potential by a displacement of the electrokinetic shear plane, the observed increase in ζ is probably due to the adsorption of highly charged positive hydrolysis products of BAS.     

高温超导体中的相分离和电荷有序

文章简要介绍了高温超导体中的相分离现象及其研究现状，同时报道了作者对Ｌａ２ＣｕＯ４体系中的相分离及电荷有序现象的研究工作．     

Thermosensitive polyalcohols: Synthesis via living cationic polymerization of vinyl ethers with a silyloxy group

Thermosensitive homopolymers and copolymers with hydroxy groups were synthesized via the living cationic polymerization of Si‐containing vinyl ethers. The cationic homopolymerization and copolymerization of five vinyl ethers with silyloxy groups, each with a different spacer length, were examined with a cationogen/Et_1.5AlCl_1.5 initiating system in the presence of an added base. When an appropriate base was added, the living cationic polymerization of Si‐containing monomers became feasible, giving polymers with narrow molecular weight distributions and various block copolymers. Subsequent desilylation gave well‐defined polyalcohols, in both water‐soluble and water‐insoluble forms. One of these polyalcohols, poly(4‐hydroxybutyl vinyl ether), underwent lower‐critical‐solution‐temperature‐type thermally induced phase separation in water at a critical temperature (T_PS) of 42 °C. This phase separation was quite sensitive and reversible on heating and cooling. The phase separation also occurred sensitively with random copolymers of thermosensitive and hydrophilic or hydrophobic units, the T_PS values of which in water could be controlled by the monomer feed ratio. The thermal responsiveness of this polyalcohol unit made it possible to prepare novel thermosensitive block and random copolymers consisting solely of alcohol units. One example prepared in this study was a 20 wt % aqueous solution of a diblock copolymer consisting of thermosensitive poly(4‐hydroxybutyl vinyl ether) and water‐soluble poly(2‐hydroxyethyl vinyl ether) segments, which transformed into a physical gel above 42 °C. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3300–3312, 2003