Synthesis and characterization of new thermally stable poly(ester‐imide)s derived from 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl and various aromatic dihydroxy compounds

A series of new alternating aromatic poly(ester‐imide)s were prepared by the polycondensation of the preformed imide ring‐containing diacids, 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl (2a) and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl (2b) with various aromatic dihydroxy compounds in the presence of pyridine and lithium chloride. A model compound (3) was also prepared by the reaction of 2b with phenol, its synthesis permitting an optimization of polymerization conditions. Poly(ester‐imides) were fully characterized by FTIR, UV‐vis and NMR spectroscopy. Both biphenylene‐ and binaphthylene‐based poly(ester‐imide)s exhibited excellent solubility in common organic solvents such as tetrahydrofuran, m‐cresol, pyridine and dichloromethane. However, binaphthylene‐based poly(ester‐imide)s were more soluble than those of biphenylene‐based polymers in highly polar organic solvents, including N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide and dimethyl sulfoxide. From differential scanning calorimetry thermograms, the polymers showed glass‐transition temperatures between 261 and 315 °C. Thermal behaviour of the polymers obtained was characterized by thermogravimetric analysis, and the 10 % weight loss temperatures of the poly(ester‐imide)s was in the range 449–491 °C in nitrogen. Furthermore, crystallinity of the polymers was estimated by means of wide‐angle X‐ray diffraction. The resultant poly(ester‐imide)s exhibited nearly an amorphous nature, except poly(ester‐imide)s derived from hydroquinone and 4,4′‐dihydroxybiphenyl. In general, polymers containing binaphthyl units showed higher thermal stability but lower crystallinity than polymers containing biphenyl units. Copyright © 2005 Society of Chemical Industry     

冶金炉渣氮化物容量研究的进展

本文总结了近年冶金炉渣氮酸盐容量的研究方法，氮在炉渣中存在形态与炉渣氧分压的关系，炉渣氮化物容量与温度及炉渣成分的关系，并给出设计钢液脱氮渣系的基本原则。     

Studies on the interactions of metal oxides and Na2 SO4 at 1100 and 1200 K in oxygen

The interaction of different metal oxides such as Co₃O₄, NiO, Al₂O₃, Cr₂O₃, Fe₂O₃ and SiO₂ with Na₂SO₄ at a temperature of 1100 and 1200 K in flowing oxygen has been studied. The thermogravimetric studies for each system were carried out as a function of Na₂SO₄ in the mixture. The presence of different constituents in the reaction products were identified by X-ray diffraction analysis and the morphologies of the reaction products were characterized using metallography and scanning electron microscopy (SEM). The formation of products was also investigated by thermodynamic computation of free energies of the reactions and the study of relevant equilibrium phase diagrams. The soluble species in the aqueous solutions of the reaction products were determined quantitatively using atomic absorption spectrophotometry. The high temperature interaction products usually contain a 3-phase structure namely, Na₂O·M₂O _x , M₂O _x and metal sulphide and/or metal sulphate. The formation of Na₂O·M₂O _x depends upon the solid state solubility of metal oxide in the molten salt at high temperatures. Under limited solubility conditions Na₂O·M₂O _x is invariably formed, but as soon as this condition is relaxed the oxide. M₂O _x , precipitates and forms a separate phase.     

Analysis of supersaturation and nucleation in a moving solution droplet with flowing supercritical carbon dioxide

A supercritical antisolvent (SAS) process is employed for production of solid nanoparticles from atomized droplets of dilute solution in a flowing supercritical carbon dioxide (SC CO₂) stream by attaining extremely high, very rapid, and uniform supersaturation. This is facilitated by a two‐way mass transfer of CO₂ and solvent, to and from the droplet respectively, rendering rapid reduction in equilibrium solubility of the solid solute in the ternary solution. The present work analyses the degree of supersaturation and nucleation kinetics in a single droplet of cholesterol solution in acetone during its flight in a flowing SC CO₂ stream. Both temperature and composition are assumed to be uniform within the droplet, and their variations with time are calculated by balancing the heat and mass transfer fluxes to and from the droplet. The equilibrium solubility of cholesterol with CO₂ dissolution has been predicted as being directly proportional to the Partial Molar Volume Fraction (PMVF) of acetone in the binary (CO₂–acetone) system. The degree of supersaturation has been simulated up to the time required to attain almost zero cholesterol solubility in the droplet for evaluating the rate of nucleation and the size of the stable critical nuclei formed. The effects of process parameters have been analysed in the pressure range of 7.1–35.0 MPa, temperature range of 313–333 K, SC CO₂ flow rate of 0.1136–1.136 mol s^?1, the ratio of the volumetric flow rates of CO₂‐to‐solution in the range of 100–1000, and the initial mole fraction of cholesterol in acetone solution in the range of 0.0025–0.010. The results confirm an extremely high and rapid increase in degree of supersaturation, very high nucleation rates and stable critical nucleus diameter of the order of a nanometre. Copyright © 2005 Society of Chemical Industry     

Organosoluble and light-colored fluorinated polyimides derived from 2,3-bis(4-amino-2-trifluoromethylphenoxy)naphthalene and aromatic dianhydrides

A novel fluorinated bis(ether amine) monomer, 2,3-bis(4-amino-2-trifluoromethylphenoxy)naphthalene, was prepared through the nucleophilic aromatic substitution reaction of 2-chloro-5-nitrobenzotrifluoride and 2,3-dihydroxynaphthalene in the presence of potassium carbonate, followed by catalytic reduction with hydrazine and Pd/C. A series of new fluorine-containing polyimides having inherent viscosities of 0.54 to 1.10 dl/g were synthesized from the diamine with various commercially available aromatic dianhydrides using a standard two-stage process with thermal imidization of poly(amic acid) films. These polyimides were highly soluble in a variety of organic solvents, and most of them afforded transparent, light-colored, and tough films with good tensile strengths. These polyimides exhibited glass transition temperatures (T_gs) of 247-300 °C and showed no significant decomposition below 500 °C under either nitrogen or air atmosphere. Except for the polyimide derived from pyromellitic dianhydride, the polyimide films were almost colorless, with an ultraviolet-visible absorption cutoff wavelength below 400 nm and low b∗ values (a yellowness index) of 10.7-41.9. These polyimides had dielectric constants of 3.09 to 3.65 (1 MHz) and moisture absorptions in the range of 0.2-0.3 wt%.     

An analysis of the electrical conductivity in BaSO4-added Ag2SO4 solid electrolyte system

The compositions (1 −x)Ag₂SO₄−(x)BaSO₄, wherex=0·01 to 0·6, were prepared by slow cooling of the melt. The extent of the solid solubility of Ba²⁺ in Ag₂SO₄ was determined by X-ray powder diffraction and scanning electron microscopy. The bulk conductivity of each sample was obtained using a detailed impedance analysis. The partial substitution of Ba²⁺ results in the enhancement of conductivity in compliance with the classical aliovalent doping theory. A simplistic model based on lattice distortion (expansion) due to partial substitution of Ag⁺ by the bigger Ba²⁺ has been considered to explain enhanced conductivity. Beyond solid-solubility limit (5·27 mole%) the BaSO₄-dispersed Ag₂SO₄ conductivity follows the usual trend seen in binary systems. An increase in conductivity in this case is discussed in the light of interfacial reactions and surface defect chemistry. The maximum conductivity in 20 mole% BaSO₄ dispersed Ag₂SO₄ is due to percolation threshold.     

Use of inverse gas chromatography to quantify interactions in amine cured epoxy resins

Flory–Huggins interaction parameters, λ, were determined for a series of probes in an amine cured epoxy resin matrix (433–493 K) and its precursors (324–363 K) by inverse gas chromatography (IGC). Hildebrand–Scatchard theory was combined with Flory–Huggins theory in order to estimate infinte dilution solubility parameters (δ₂) for the matrix and its precursors at 298 K. It was shown that the value of the solubility parameter for the cured resin matrix lies between those of its precursors. Compared to the majority of published work, an unusual aspect of this application of IGC is that solubility parameters have been determined when the stationery phases are (i) small molecules and (ii) a highly crosslinked polymer. Moreover, all possible attempts have been made to ensure equilibrium conditions between probe and stationary phase, and compensation for asymmetry of peak profile has been applied in determining δ₂. The solubility parameters estimated by IGC are in good agreement with those calculated by other methods.     

Investigation of Scale Formation in Heat Exchangers of Phosphoric Acid Evaporator Plants

The primary problem in concentrating phosphoric acid is due to fouling on the tube‐side of the heat exchangers of the evaporator units. Scaling on the heat transfer surfaces occurs because of high supersaturation of phosphoric acid liquor with respect to calcium sulphate. A review of the existing literature reveals that no information is available on heat transfer and on crystallization fouling of industrial phosphoric acid solutions. In this investigation, the solubility of different calcium sulphate types in phosphoric acid solution was studied and its dependency on acid concentration and temperature was investigated. A large number of fouling experiments were carried out in a side‐stream of a phosphoric acid plant at different flow velocities, surface temperatures and concentrations to determine the mechanisms, which control the deposition process. After identifying the effects of operational parameters on the deposition process, a model was developed for prediction of fouling resistances. The reaction of calcium sulphate crystallization followed a second order rate with respect to the supersaturation. The activation energy evaluated for the surface reaction of the deposit formation was found to be 57 kJ/mol. The predicted fouling resistances were compared with the experimental data. Quantitative and qualitative agreement between measured and predicted fouling rates is good.     

Effect of polymerization conditions on o‐phenylenediamine and o‐phenetidine oxidative copolymers

A series of new o‐phenylenediamine (OPD)/o‐phenetidine (PHT) copolymers with partly phenazine‐like structures has been successfully synthesized at three polymerization temperatures by chemically oxidative polymerization in four different polymerization media. The molecular structures and properties of the resulting OPD/PHT polymers were investigated by IR, UV–vis and high‐resolution ¹H NMR spectroscopies, and DSC, in order to ascertain the effect of reaction temperature, comonomer ratio and acid medium. The copolymerization mechanism of OPD with PHT monomers has been proposed. It is found that the statistical OPD/PHT copolymer obtained at a temperature of 118 °C has a higher degree of polymerization than that obtained at 12–17 °C. The OPD content in the copolymers calculated from NMR spectroscopic analysis is higher than that in the feed OPD content, whereas the OPD content calculated from element analysis is slightly lower than the feed OPD content. It can be predicted that denitrogenation takes place in the OPD units during the polymerization process at OPD/PHT molar ratios of 90/10 and 100/0. These OPD/PHT copolymers exhibit a much better solubility than the OPD homopolymer, hence suggesting an incorporation of PHT units into the phenazine structure of the homopolymer. The thermal behavior of the copolymers was also studied. Copyright © 2004 Society of Chemical Industry     

2，6-萘二甲酸二甲酯在有机溶剂中溶解度的测定与关联

Solubility of dimethyl-2,6-naphthalene dicarboxylate in acetic acid, N,N-dimethylfonnamide, N,N-dimethyl acetamide, dimethyl sulphoxide, and N-methyl-2-ketopyrrolidine were determined using a dynamic method. The measured systems were correlated by UNIFAC group contribution method. A new main group （aromatic ester, ACCOO） was defined to express the activity coefficients of the aromatic ester. New interaction parameters of the ACCOO group were expressed as the first-order function of temperature and were determined from the experimental data. The calculated results for the new interaction parameters were satisfactory. The measured systems were also correlated with the Wilson and 2-h models, and the results were compared with those of the UNIFAC model.