Gas permeability and permselectivity of photochemically crosslinked copolyimides

A series of copolyimides were prepared from 2,4,6-trimethyl-1,3-phenylenediamines (3MPDA), 3,3',4,4'-benzophenone tetracarboxyl dianhydride (BTDA), and pyromellitic dianhydride (PMDA). Modification of the copolyimides by ultraviolet irradiation were carried out. Gas permeabilities of H-2, O-2, and N-2 through the copolyimides and photochemically crosslinked copolyimides were measured at temperatures from 30 to 90 degrees C. The relationships between gas permeabilities and temperature are in agreement with the Arrhenius equation. The structure of photochemically crosslinked copolyimides were characterized by Fourier transform infrared and gel measurement methods. Linear relationships between both log P and E-p and the volume fraction of PMDA-3MPDA exist. Photochemically crosslinking modification result in a decrease in gas permeability and an increase in E-p and alpha(H-2/N-2) for all the copolyimides. For H-2/N-2 separation, photochemically crosslinked copolyimides are of higher gas permeabilities and permselectivities simultaneously than normal polyimides. (C) 1999 John Wiley & Sons, Inc.

Positive- and negative-ion matrix-assisted laser desorption/ionization mass spectrometry of saccharides

Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) of oligosaccharides and polysaccharides has been investigated in detail, It is demonstrated that cationized species of oligosaccharides, [M+Na](+) and [M+K](+), are dominant products under the MALDI condition, and negative ions of oligosaccharides are not formed to any significant extent in this process, The molecular masses of polysaccharides are similarly determined by positive- and negative-ion MALDI-MS with the help of column chromatography. The distinction between positive- and negative-ion MALDI mass spectra of oligo-and polysaccharides indicates that the MALDI processes for saccharides vary with molecular mass. The matrix plays a more important role in the ionization process for oligosaccharides, while in the desorption process for polysaccharides. (C) 1998 John Wiley & Sons, Ltd.

Color filters with negative birefringence for liquid crystal display use

We have developed a special color film with negative birefringence, which can work as a color filter and a viewing angle extension film for liquid crystal displays (LCDs). A high-performance polyimide (PI), which can be dissolved in the usual organic solvent and shows negative birefringence after lamination, was synthesized to fabricate the film. By mixing PI with suitable proportions of green, blue or red pigment in the solvent, then laminating them onto a glass substrate, we obtained color films with good transmission spectra and suitable chromatic coordinates. The results of our experiments show that the color filters still have negative birefringence but a little lower than that of the pure PI film. and can therefore work as compensation films for normal white twist nematic liquid crystal displays (TN-LCD).

Structure/permeability and permselectivity relationship of polyetherimides from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride .2.

Gas permeability coefficients of a series of aromatic polyetherimides, which were prepared from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride (HQDPA) with various aromatic diamines, to H-2, O-2 and N-2 have been measured under 7 atm and at the temperature range 30-100 degrees C. A significant change in the permeability and permselectivity resulting from the systematic variation in chemical structure of the polyetherimides was found. Among the polyetherimides, that were prepared from phenylenediamine and methyl substituted phenylenediamines, the increase of permeability is accompanied by a decrease of permselectivity. The polyetherimides that were prepared from 3,5-diaminobenzoic esters have lower permselectivity than the others. However, the polyetherimide from 3,5-diaminobenzoic acid possesses much higher permselectivity than the others due to cross-linking. Copyright (C) 1996 Elsevier Science Ltd

Gas permeability in polyimides from oxydianiline and isomeric thiaphthalic dianhydride or 1,4-bis(dicarboxyphenoxy) benzene dianhydride

The gas permeability and permselectivity properties were investigated of polyimides, prepared from 3,3',4,4'- and 2,2',3,3'-thiaphthalic dianhydride (p-TDPA and m-TDPA, respectively), or 1,4-bis(3,4-dicarboxyphenoxy)- and 1,4-bis(2,3-dicarboxyphenoxy) benzene dianhydride (p-HQDPA and m-HQDPA, respectively), and 4,4-oxydianiline. The polyimides prepared from meta-dianhydrides, which have lower chain-segment packing density, possess higher permeability and lower permselectivity than those prepared from para-dianhydrides. Copyright (C) 1996 Elsevier Science Ltd.

Effects of molecular structure on the permeability and permselectivity of aromatic polyimides

Permeability coefficients of H-2, O-2, and N2 were measured under 10 atm at the temperature from ambient temperature up to 150 degrees C in a series of structurally different aromatic homo- and copolyimides, which were prepared from 4,4'-oxydianiline (ODA) or 4,4'-methylene dianiline (MDA) with various aromatic dianhydrides. The study shows that the molecular structure of the polyimides strongly influences gas permeability and permselectivity. As a result, the permeability coefficients of the polyimide membranes for each gas vary by over two orders of magnitude. In general, among the polyimide membranes studied, the increase in permeability of polymers is accompanied by the decrease in permselectivity, and the MDA-based polyimide membranes have higher permeability than ODA-based ones. Among the polyimides prepared from bridged dianhydrides, the permeability coefficients to H-2, O-2, and N-2 are progressively increased in the order BPDA < BTDA < ODPA similar to TDPA < DSDA ( SiDA < 6FDA, while H-2/N-2 and O-2/N-2 permselectivity coefficients are progressively decreased in the same order. The copolyimide membranes, which were prepared from 3,3',4,4' biphenyltetracarboxylic dianhydride (BPDA), bis(3,4-dicarboxyphenyl)dimethylsilane dianhydride (SiDA), and ODA, have favorable gas separation properties and are useful for H-2/N-2 separation applications. (C) 1996 John Wiley & Sons, Inc.

Structure/permeability and permselectivity relationship of polyetherimides from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride .1.

Gas permeability coefficients of a series of aromatic polyetherimides, which were prepared from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride (HQDPA) and various aromatic diamines, to H-2, CO2, O-2, N-2 and CH4 have been measured under 7 atm pressure and over the temperature range 30-150 degrees C. A significant change in permeability and permselectivity, which resulted from a systematic variation in chemical structure of the polyetherimides, was found. Generally, increases in permeability of the polyetherimides are accompanied by decreases in permselectivity. The order of decrease of the permeability coefficients is as follows: HQDPA-IPDA > HQDPA-DDS > HQDPA-MDA > HQDPA-ODA > HQDPA-DABP > HQDPA-BZD. However, HQDPA-DMoBZD and HQDPA-DMoMDA, with bulky methoxy side-groups on the aromatic rings of the diamine residue, display both high permeability coefficients and high permselectivity. The favourable gas separation property, excellent thermal and chemical stability, and high mechanical strength make HQDPA-DMoBZD and HQDPA-DMoMDA promising candidates for membrane-based gas separation applications.

Structure/permeability and permselectivity relationship of polyetherimides from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride .3.

Gas permeability coefficients of a series of aromatic polyetherimides prepared from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride (HQDPA) and four (methylene dianiline)s with a methyl side group to H-2, CO2, O-2, N-2, and CH4 were measured under 7 atm and within a temperature range from 30 to 150 degrees C. The gas permeabilities and permselectivities of these polymers were compared with those of the HQDPA-based polyetherimides from methylene dianiline (MDA) and isopropylidene dianiline (IPDA). The number and position of the methyl side groups on the benzene rings of the diamine residues strongly affect the gas permeabilities and permselectivities of the HQDPA-based polyetherimides. The gas permeability of the polyetherimide progressively increases with an increase in the number of the methyl side groups. Both the gas permeability and permselectivity of the polyetherimides with methyl side groups are higher than those of HQDPA-MDA. The polyetherimide prepared from 3,3'-dimethyl 4,4'-methylene dianiline (DMMDA1) possesses both higher permeability and permselectivity than the polyetherimides prepared from 2,2'-dimethyl 4,4'-methylene dianiline (DMMDA2). However, two of the polyetherimides prepared 2,2',3,3'-tetramethyl 4,4'-methylene dianiline (TMMDA1) or 2,2', 5,5'-tetramethyl 4,4'-methylene dianiline (TMMDA2) possess almost the same gas permeability and permselectivity.

AN EXTENSION OF THE METHOD FOR PREDICTING PERMEABILITY THROUGH POLYMER MEMBRANES FROM SIMPLE GASES TO WATER-VAPOR

It is found that there is a linear relationship between log P-w, and the parameter term V-f/0.5 E(coh) [1+(delta(w) - delta(p))(2)/delta(p)(2), from the water permeability (P-w) data of 21 polymers covering 4 orders of magnitude. This correlation may be useful in choosing membrane materials for dehumidification of gases.

A SIMPLE METHOD FOR PREDICTION OF GAS-PERMEABILITY OF POLYMERS FROM THEIR MOLECULAR-STRUCTURE

A method for the prediction of gas permeabilities (P) through polymers from their chemical structure has been developed on the basis of the ratio of molar free volume to molar cohesive energy, V(f)/E(coh). The permeation of small gas molecules through polymer membranes is dependent on the chain packing density measured by V(f) and segmental motion of polymer chains measured by E(coh). But no simple relationship between P and V(f) or E(coh) alone was found. The permeability data of more than 60 polymers covering 7 orders of magnitude for six gases have been treated with linear regression analysis. All plots of log P vs. V(f)/E(coh) gave good straight lines. It is also found that a linear relationship holds when plotting both the intercepts and slopes of log P vs. V(f)/E(coh) lines against square of the diameters of gas molecules. Therefore, the permeabilities of all the non-swelling gases through a great variety of polymers can be estimated using two correlations above. Moreover, this method is more accurate than others in the literature and may found useful for the selection of gas separation or barrier membrane materials.

A novel anti-tumor protein extracted from Meretrix meretrix Linnaeus induces cell death by increasing cell permeability and inhibiting tubulin polymerization

Discovery and development of new pharmaceuticals from marine organisms are attracting increasing interest. Several agents derived from marine organisms are under preclinical and clinical evaluation as potential anticancer drugs. We extracted and purified a novel anti-tumor protein from the coelomic fluid of Meretrix meretrix Linnaeus by ammonium sulphate fractionation, ion exchange and hydrophobic interaction chromatography. The molecular weight of the highly purified protein, designated MML, was 40 kDa as determined by SDS-PAGE analysis. MML exhibited significant cytotoxicity to several cancer cell types, including human hepatoma BEL-7402, human breast cancer MCF-7 and human colon cancer HCT116 cells. However, no inhibitory effect was found when treating murine normal fibroblasts NIH3T3 and benign human breast MCF-10A cells with MML. The cell death induced by MML was characterized by cell morphological changes. The induction of apoptosis of BEL-7402 cells by MML was weak by DNA ladder assay. The possible mechanisms of its anti-tumor effect might be the changes in cell membrane permeability and inhibition of tubulin polymerization. MML may be developed as a novel, highly selective and effective anti-cancer drug.

Global negative vegetation feedback to climate warming responses of leaf litter decomposition rates in cold biomes

Whether climate change will turn cold biomes from large long-term carbon sinks into sources is hotly debated because of the great potential for ecosystem-mediated feedbacks to global climate. Critical are the direction, magnitude and generality of climate responses of plant litter decomposition. Here, we present the first quantitative analysis of the major climate-change-related drivers of litter decomposition rates in cold northern biomes worldwide. Leaf litters collected from the predominant species in 33 global change manipulation experiments in circum-arctic-alpine ecosystems were incubated simultaneously in two contrasting arctic life zones. We demonstrate that longer-term, large-scale changes to leaf litter decomposition will be driven primarily by both direct warming effects and concomitant shifts in plant growth form composition, with a much smaller role for changes in litter quality within species. Specifically, the ongoing warming-induced expansion of shrubs with recalcitrant leaf litter across cold biomes would constitute a negative feedback to global warming. Depending on the strength of other (previously reported) positive feedbacks of shrub expansion on soil carbon turnover, this may partly counteract direct warming enhancement of litter decomposition.

煤系地层三维三分量地震数据解释方法研究

Conventional 3D seismic exploration cannot meet the demand of high yield and high efficiency safe production in coal mine any more. Now it is urgent to improve the discovery degree of coal mine geological structures for coal production in China. Based on 3D3C seismic exploration data, multi-component seismic information is fully excavated. First systematic research on 3D3C seismic data interpretation of coal measure strata is carried out. Firstly, by analyzing the coal measure strata, the seismic-geologic model of coal measure strata is built. Shear wave logging is built by using regression analysis. Horizon calibration methods of PP-wave and PS-wave are studied and the multi-wave data are used together to interpret small faults. Using main amplitude analysis technology, small faults which cannot be found from PP-wave sections can be interpreted from the low frequency PS-wave sections. Thus, the purpose to applying PS-wave data to fine structure assistant interpretation is achieved. Secondly, PP- and PS-wave post-stack well constrained inversion methods of coal measure strata are studied. Joint PP- and PS-wave post-stack inversion flow is established. More attribute parameters, which are applied in fine lithology interpretation of coal measure strata, are obtained from combinations of the inversion results. Exploring the relation between rock with negative Poisson’s ratio and anisotropy, fracture development in coal seam are predicted. Petrophysical features of coal measure strata are studied, and the relations between elastic parameters and lithology, fluid and physical properties are established. Inversions of the physical parameters such as porosity, permeability and water saturation, which reflect lithology and fluid property, are obtained. Finally, the approaches of shear wave splitting and Thomsen parameters inversion, which provide new ideas for seismic anisotropy interpretation of coal measure strata, are studied to predict fracture development. The results of practical application indicate that the methods in this paper have good feasibility and applicability. They have positive significance for high yield and high efficiency safe production in coal mine.

塔里木盆地寒武－奥陶系白云岩类型、成因机理及其孔隙性研究

Cambrian-Ordovician dolostones in Tarim Basin are hydrocarbon reservoir rocks of vital importance. Under the guidance of the theories of sedimentology and the sedimentology of carbonate reservoir, based on the first-hand qualitative and quantitative data especially, combined with micro-study, geochemical and reservoir capacity analysis, and precursor research, the origin and reservoir characteristics of the dolostones were discussed. Based on detailed petrographic investigations, four types of dolostone have been recognized, which are, respecitively, mud-silt-sized dolostones, algal laminated dolostones (ALD), prophyritic dolostone, and neomorphic dolostone. Mud-silt-sized dolostones always presents as laminas together with evaporated signatures, its REE patterns and ΣREE are all close to that of the finely crystalline limestone. This kind of dolomite probably experienced relatively low fluid-rock ratio during diagenesis was formed in hypersaline and oxidizing environment and involved fast dolomitization process. It was dolomitized by evaporated seawater in sabkha environment.The main primary fabrics of algal lamination in algal laminated dolomite (ALD) can still be identified and its ΣREE (21.37) is very close to that of algae. This reveals that ALD was dolomitized during early diagenesis and algae possibly played an important role. The ALD was formed under mediation of organic matter and Mg2+ were supplied by magnesium concentrated algal laminites and sea water. Prophyritic dolostones presents mainly as patchy occurrence and yield the lowest δ13C and Z value. Its ΣREE is much less than that of the finely crystalline limestone. These characteristics reveal that the cloudy cores were dolomitized in shallow early diagenetic environments by pore fluids riched in Mg2+. Whereas the clear rims were likely formed in subsequent burial into deeper subsurface environments, and the Mg2+ needed for further dolomitization possibly was supplied by the transformations of clay minerals. Neomorphic dolostones consist of coarse, turbid crystals and exhibits sucrosic and mosaic textures. It has highest Fe2+ contents and average homogeneous temperature (110.2℃). Collectively, these characteristics demonstrate that the neomorphic dolostones was likely formed by recrystallization of pre-existing dolomites during deep burial. The ΣREE of the four types of dolostone distinctly differentiates from each other. However, their REE patterns are all enriched in LREE, depleted in HREE and have Eu negative anomalies. Its ΣREE 13.64 ppm, less than 1/4 of finely crystalline limestone, and ranks the lowest in the 4 types.These characteristics are comparable to those of finely crystalline limestone, and are mainly infuenced by the sea water. These four types of dolostone show similar REE mobility behaviour and no significant fractionation, althouth they have been subjected to evidently different diageneses. Seven main pore types are identified in the dolostones , which are fenestral, moldic, intercrystal, dissolved，breccia, dissolved breccia and stylolite pores. Fenestral pores are primary and the others are secondary. The dissolved pores and intercrystal pores are the most important reservoir spaces and followed by breccias and dissolved breccia pores, and the moldic and fenestral pores are less important. Stylolites can enhance permeability of reservoir rocks in one hand, for the other hand, the capacity of reservoir and permeability are enhanced and then better reservoir rocks can be formed when they are combined with patchy dolostones. The relationship between porosity and the type of dolostones is that the dissolved neomorphic dolostones have the highest porosity of 3.65%, than followed by dissolved Mud-silt-sized dolostones of 3.35%. The mud-silt-sized dolostones without dissolution have the lowest porosity of 0.90%. Moreover, the porosity of prophyritic dolostones and the neomorphic dolostones without dissolution are lower, respectively 1.675% and 1.41%. Although algal laminated dolostones consist of euhedral crystals and riched in intercrystal pores, its porosity just yields 1.20%. The relationship between permeability and the type of dolostones is that that algal laminated dolostones have the highest permeability of 0.462mD and followed by 0.065mD of prophyritic dolostones. Dissolution have no significant influence on the permeability of neomorphic dolostones and this presented by the permeability of dissolved and non-dissolved are very close, respectively 0.043mD and 0.062mD. No matter dissolved or not, mud-silt-sized dolostones are much less permeable. The permeability of non-dissolved and dissolved are 0.051mD and 0.016mD. Collectively, in the study area, neomorphic dolostones can form high quality reservoir.