Effect of hydrophobic hexafluoroisopropylidene group on the water sorption behaviors of rigid poly(p‐phenylene pyromellitimide) polyimide thin films

We prepared poly(p‐phenylene pyromellitimide) (PMDA–PDA), poly(p‐phenylene 4,4′‐hexafluoroisopropylidene diphthalimide), and their copolyimides with various compositions to explore the relationship between the water sorption and structure. The water sorption behaviors were gravimetrically investigated as a function of composition and temperature and interpreted with a Fickian diffusion model in films. Overall, the water sorption behaviors were strongly dependent on the changes in morphological structure, which originated from the variations in composition. When the content of the bulky hexafluoroisopropylidene group (6FDA) was increased, the water uptake decreased from 5.80 to 3.18 wt %, whereas the diffusion coefficient increased from 3.6 × 10^?10 to 11.3 × 10^?10 cm²/s. The relatively high water uptake in the PMDA–PDA polyimide film was successfully healed by the incorporation of 6FDA, which may have resulted from the increases in the intermolecular packing order and hydrophobicity. The degree of orientation and crystallinity, which are in‐plane characteristics, were directly correlated to the diffusion coefficient and activation energy in the polyimide film. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3442–3446, 2003     

Kinetic study of radical polymerization. II. Solid‐state bulk polymerization of sodium methacrylate by differential scanning calorimetry

The solid‐state radical polymerization of sodium methacrylate was investigated. It was initiated by azobisisobutyronitrile, which was used as a radical initiator. Differential scanning calorimetry (DSC) was used to observe the endothermic and exothermic transitions during the polymerization reaction. Structural studies were performed with the DSC thermograms and Fourier transform infrared and ultraviolet–visible spectra, and all of the results confirmed the progress of the reaction. The obtained data revealed that the polymerization reaction proceeded completely with a 100% conversion. ΔH of this reaction was calculated with various amounts of the initiator, and the peak temperatures were determined at different heating rates. The activation energy (19.7 kcal mol^?1) was also obtained by the Kissinger method for this type of solid polymerization reaction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1648–1654, 2003     

纳米碳酸钙的表面活化改性研究

本文主要介绍通过加入特定的表面改性剂,制得了表面改性的活性碳酸钙.并对活化过程中的一系列影响因素,如活化温度、活化时间、碳酸钙悬浊液浓度、表面改性剂用量进行了研究.     

Methane activation without using oxidants over Mo/HZSM-5 zeolite catalysts

The effect of Mo loading, calcination temperature, reaction temperature and space velocity on the catalytic performance of methane dehydrogenation and aromatization without using oxidants over Mo/HZSM-5 has been studied. The XRD and BET measurements show that Mo species are highly dispersed in the channels of the HZSM-5 zeolite, resulting from the interaction between the Mo species and the zeolite, which also leads to a decrease in its crystallinity. The Brønsted acidity, the channel structure and the state and location of Mo species in the zeolite seem to be crucial factors for its catalytic performance. It was found that 2% Mo/HZSM-5 calcined at 773 K showed the best aromatization activity among the tested catalysts, the methane conversion being 9% at 1013 K with the selectivity to aromatics higher than 90%. The experimental results obtained from the variation of space velocity gave evidence that ethylene is an initial product. On the basis of these results a possible mechanism for methane dehydrogenation and aromatization has been proposed in which both the heterolytic splitting of methane in a solid acid environment and a molybdenum carbene-like complex as an intermediate are of significance.     

A vibrational study of the activation sequence of C–H and C–C bonds of isobutene and 1-butene on Mo(110) and (4 × 4)-C/Mo(110) surfaces

The thermal decomposition pathways of isobutene and 1-butene on both Mo(110) and 4 × 4-C/Mo(110) surfaces have been studied using high-resolution electron energy loss spectroscopy (HREELS) in order to highlight the substantially different activities of these two surfaces towards the cleavage of C–H and C–C bonds. On clean Mo(110), the CH₂ group of isobutene decomposes upon heating to 150 K, producing either a /-bonded isobutenylidene [(CH₃)₂CCH] species or a 1,1-di-/-bonded isobutenyl [(CH₃)₂CC] species. Upon further heating, extensive C–H bond scission occurs to form hydrocarbon fragments which do not contain CH₃ or CH₂ groups, but appear to have largely intact carbon skeletons. By contrast, isobutene is molecularly adsorbed on the carbide-modified surface at 150 K. Further heating produces isobutylidyne [(CH₃)₂HCC] by 300 K, which subsequently decomposes via C–C bond scission to generate surface methyl groups. The different activation sequence of the C–H and C–C bonds of isobutene on clean and carbide-modified Mo(110) surfaces is also qualitatively confirmed by comparative studies of 1-butene on the two surfaces.     

Pulse study of methane partial oxidation to syngas over SiO2-supported nickel catalysts

Methane was pulsed over pure CuO and NiO as well as Cu/La₂O₃ and Ni/La₂O₃ catalysts at 600° C. Results indicate that the mechanisms for methane activation over copper and nickel are quite different. Over CuO, methane is converted to CO₂ and H₂O, most likely via the combustion mechanism; whereas metallic copper does not activate methane. Over NiO in the presence of metallic nickel sites, methane activation follows the pyrolysis mechanism to give CO, CO₂, H₂ and H₂O. Similar results were obtained over the Cu/La₂O₃ and Ni/La₂O₃ catalysts. XRD investigations indicate that copper and nickel existed as CuLa₂O₄ and LaNiO₃ respectively in the La₂O₃-supported catalysts. The effect of La₂O₃ on the activation of methane is discussed.     

温度和氧浓度对PX氧化的影响

根据不同温度、氧浓度下实测的PX液相催化氧化各中间组分浓度 时间关系,采用双曲型的动力学模型拟合实验数据,得到了各步反应活化能数据和速率常数与氧浓度的关系式。结果说明,PT酸氧化为4 CBA这一步的活化能最大,是整个连串反应过程的速率控制步骤;反应有一个氧浓度门槛值,在此值以上,反应速率不再明显增大,在此值以下,反应速率随氧浓度增大而增大。工业尾氧体积分数一般在4%～5%,相应的反应速率在最大速率的90%左右。     

可发泡性酚醛树脂的合成研究

考查了可发泡性酚醛树脂的合成条件,如反应时间、温度和催化剂用量等对树脂活性、物理以及酚醛泡沫塑料容重和表观品质的影响,结果表明:催化剂用量越大,树脂粘度越大,泡沫固化时间越长;反应时间介于65～95min,泡沫塑料容重和表观品质较好;用加热板测定了合成的可发泡性树脂的固化速度,并求出固化反应活化能。     

CaO对CaO-Al2O3-SiO2微晶玻璃晶化过程活化能的影响

CaO对CaO-Al2O3-SiO2系统微晶玻璃的烧结及析晶性能有较大影响,从而影响了微晶玻璃的结构及性能.本文运用DTA、烧结收缩率分别测定了CaO-A12O3-SiO2系统微晶玻璃的烧结活化能及析晶活化能,研究了这两者的变化趋势.     

Reaction kinetics of rye straw for thermnochemical conversion

Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were conducted on two common types of rye straws (Danko and Kustro) at a heating rate of 20°C/min in an oxidizing atmosphere (15% oxygen and 85% nitrogen, by volume) between ambient temperature and 700°C. The two step nature of the TGA curves and the dual peak characteristics of the DTA curves showed that rye straw had two distinct reaction zones. The initial degradation temperatures, the residual mass at 700°C, the thermal degradation rates in the first and second reaction zones and the kinetic parameters of each reaction zone (order of reaction, activation energy and pre-exponential factor) were determined. Higher thermal degradation rates were observed in the first reaction zone as compared to those in the second reaction zone.