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101.
Surface modification of poly [1-(trimethylsilyl)-1-propyne] (PTMSP) membranes bybromine vapor has been studied. It is shown that Br/C atomic ratio at the surfaces increased withthe time of bromination until about 60 min, then it reached a plateau. The results of XPS and IRstudies indicated that the addition of bromine to double bonds and the replacement of H on CH_3 bybromine had taken place so that a new peak at 286.0 eV (C--Br)in C_(1s) spectra and some newbands, e. g. at 1220 and 580cm~(-1) in IR spectra were formed. The fact,t Po_2, permeability ofoxygen, decreased and α_(O_2/N_2), separation factor of oxygen relative to nitrogen, increased withbromination time, shows that surface modification of PTMSP by bromine may be an efficient approach to prepare PTMSP membranes used for practical gas separations. 相似文献
102.
The paper presents a new method for the generation of acetaldehyde in the amounts that allow to calibrate the measuring system. The method is based on thermal decomposition of surface compounds at the range 130-190 °C, in which an acetaldehyde as the decomposition product is released. The synthetic pathway leading to the desired surface compounds is described. Investigations demonstrated that the synthesis of the compounds on the surface of the support material (silica gel) was carried out homogeneously. The technique proposed was used for the generation of gaseous standard mixtures containing acetaldehyde for the calibration of a thermal desorber-gas chromatograph-flame ionization detector system. 相似文献
103.
The high-performance liquid chromatographic behavior of some basic drugs was studied on a n-octadecylphosphonic acid modified magnesia-zirconia (C18PZM) stationary phase. The effect of mobile phase variables such as methanol content, ionic strength, and pH on their chromatographic behavior was investigated. The retention mechanism of basic drugs on the stationary phase was elucidated. The results indicate that both hydrophobic and cation-exchange interactions contribute to solute retention under most chromatographic conditions. The inherent Br?nsted-acid sites and also the adsorbed Lewis base anionic buffer constituents on accessible ZM surface Lewis acid sites play a role in the retention of ionized solutes by cation-exchange interaction. However, especially at high mobile phase pH, the retention of basic drugs depends mainly on hydrophobic interactions between solutes and support. Separations of the basic drugs on the C18PZM phase by a predominantly reversed-phase retention mode were very promising. The mixed-mode retention feature on this phase, as a result of the adsorbed Lewis base anionic buffer constituents acting as sites for cation-exchange, could also be very useful, e.g. for enhancing the chromatographic selectivity of such analytes. The C18PZM seems to be an excellent alternative to silica-based reversed-phase stationary phase for the separation of strongly basic solutes. 相似文献
104.
N,N-Diethyldithiocarbamate functionnalized 1,4-polyisoprenes were prepared from 1,4-polyisoprenes (natural or synthetic). The syntheses were performed by nucleophilic addition of N,N-diethyldithiocarbamate salts upon oxirane rings of epoxidized units according to a SN2 mechanism with ring opening. Studies on model molecules of epoxidized 1,4-polyisoprene units (1,2-epoxy-1-methylcyclohexane and 4,5-epoxy-4-methyloctane) were previously achieved to develop the procedure. The best yields were obtained at low temperature in polar medium, and more especially in water with sodium N,N-diethyldithiocarbamate (DEDT-Na) as reagent. A diastereospecific addition was noted when reaction was performed in water with DEDT-Na. Afterwards, the developed procedure was successfully generalized to epoxidized synthetic polyisoprenes and epoxidized natural rubber (in THF, then in latex medium). Excellent results were obtained in latex medium with epoxidized natural rubber (ENR) latices. As with the models, a diastereospecific addition of sodium N,N-diethyldithiocarbamate trihydrate onto epoxidized 1,4-polyisoprene units of ENR was observed at the condition to bring the latex medium to pH 8 before introduction of DEDT-Na. Influence of temperature, drc, and DEDT-Na concentration were successively examined to determine the best conditions of the addition on ENR latices. 相似文献
105.
Summary This paper presents a continuation of our research dedicated to solid-adsorbent surface modification with what are commonly regarded as volatile and easily eluted organic compounds. Two porous adsorbents were used: natural zeolite (clinoptilolite) and alumina, while the adsorbates employed were n-hepatane and benzene. The results show that a simple injection of volatile adsorbate greatly alters the solid surface adsorption properties. The consequences of volatile modifier application are discussed on the grounds of adsorption isotherms determined at 313K. Possible implications to the tailor made adsorbents are outlined as well.Part I, J. Chromatogr.442, 105 (1988) 相似文献
106.
A natural CXN zeolite (stilbite, type code-STI) discovered in China was modified with NH4^ exchange by using ammonium salt and calcinations (procedure Ⅰ), or with NH4 exchange followed by treatment with acid (procedure Ⅱ). The coordination state of Si and A1 atoms in the framework, the property of ion exchange, and the adsorption of the H-STI zeolite samples prepared by different modification procedure were investigated with XRD,EDX,^29Si and ^27Al MAS NMR, Ag^ ion exchange and Ne adsorption. The results of the investigations indicate that different procedure of the modification made variety on the distribution of the framework Si atoms and A1 atoms,the content of non-framework aluminum, and the blocking channels and the shielding effect to the positions of the exchangeable cations. The H-STI zeolite prepared by the procedure Ⅱ possesses high ion exchange capacity, open and perfect pore system, and high thermal stability. 相似文献
107.
Xiao Lian Zhang Joseph T. Hupp Gerald D. Danzer 《Journal of Electroanalytical Chemistry》1995,380(1-2)
The comparative interfacial oxidation kinetics of the approximate structural isomers trans-(O)2ReV(py)+4 and cis-(O)2ReV(bpy)(py)+2 (py, pyridine; bpy, 2,2′-bipyridine) have been assessed in aqueous solution via conventional cyclic voltammetry at a highly ordered pyrolytic graphite (HOPG) electrode. HOPG was employed because of its known propensity to diminish interfacial electron transfer (ET) rates (by ca. three to four orders of magnitude) and because of a probable lack of importance of kinetic work terms (diffuse double-layer corrections). Measured rates for the trans complex exceed those for the cis by about a factor of 3. Expressed as an effective activation Gibbs energy difference ΔG*, this corresponds to a cis-trans difference of ca. 3 kJ mol−1. The actual vibrational barriers to ET have determined from a combination of published X-ray structural results (trans complex) and new resonance Raman results (cis complex). The values are 0.6 kJ mol −1 for the trans oxidation and 4.4 kJ mol−1 for the cis oxidation (i.e. close to the barrier difference inferred from rate measurements). Further analysis shows that most of the barrier difference is associated with displacement of a (predominantly) Re-N(bpy) stretching mode found only in the cis system. Differences in metal-oxo displacements (cis > trans) are also implicated. 相似文献
108.
Chemical modification of sugarcane bagasse was achieved by esterification with phthalic anhydride in pyridine after ultrasound irradiation. The parameters including ultrasonic irradiation time 0-40 min, phthalic anhydride dosage 2.5-7.5 g, reaction time 30-150 min, and reaction temperature 80-115 °C were optimised and the extent of phthalation was measured by weight percent gain. It was found that degradation of the cell wall polymers occurred at higher temperature (>90 °C) under the experimental conditions used.FT-IR and CP/MAS 13C NMR spectroscopy studies also clearly produced evidence for phthalation reaction. The phthalated bagasse preparations showed decreased thermal stability after chemical modification. 相似文献
109.
Bing Zhou 《European Polymer Journal》2004,40(10):2357-2363
CaCO3/PEEK (poly-ether ether ketone) composites were prepared on a twin-screw extruder with different mass ratio of CaCO3/PEEK from 0% to 30%. Four types of particles were used as filler in PEEK matrix. The influence of surface treatment with sulfonated PEEK (SPEEK) of the particles on the mechanical and thermal properties of the composites was studied. The experiments included tensile tests, flexural tests, notched Izod impact tests, TGA, DSC and SEM. The modulus and yield stress of the composites increased with CaCO3 particles loadings. This increase was attributed to the bonding between the particles and the PEEK matrix, as can be proved by the SEM pictures of tensile fracture surface of the composites. The impact strength of the composites was modified by the SPEEK coated on the CaCO3 particle surface. DSC experiments showed that the particle content and surface properties influenced the glass transition temperature (Tg) and melting temperature (Tm) of the composites. The Tg increased with the content of fillers while Tm decreased. In this study the fillers treated were found to give better combination properties, which indicated that SPEEK played a constructive role in the CaCO3/PEEK composites. 相似文献
110.