Synthesis,characterization, and thermal properties of alternate copolymers containing N,N′‐bis(diphenylsilyl)tetraphenylcyclodisilazane

Hexamethyldisilazane was used as the starting material to synthesize N,N′‐bis(hydroxydiphenylsilanyl)tetraphenylcyclodisilazane (BHPTPC). By condensation polymerization of BHPTPC with α,ω‐bis(dialkylamino)dimethylsiloxane, a series of alternate copolymers containing N,N′‐bis(diphenylsilyl)tetraphenylcyclodisilazane was synthesized. GPC studies show that the highest molecular weight was obtained at a ratio of 1.005 : 1 (BHPTPC: α,ω‐bis(dimethyl amino)dimethylsiloxane). Data of DSC indicate that the temperature of glass transition (T_g) and temperature of melting point (T_m) decreased with the increasing of dimethylsiloxane segments units. Three stages of degradation were found in the thermogravimetric analysis curves. The activation energy of the copolymer (with m = 2, 3, and 7) was calculated by using Flynn–Wall–Ozawa method. The activation energy of the copolymer with m = 2, 3, and 7 at second stage is 214, 211, and 184 kJ/mol, respectively. Isothermal gravimetric analysis shows that for the same temperature and the same time, the weight loss of the alternate copolymer was greatly less than that of common polydimethylsiloxane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 611–617, 2007     

臭氧氧化法除地表水有机物试验研究

本文阐述臭氧化法除地表水有机物的重要意义，实验结果表明：臭氧氧化有机物的总氧化速率受活化控制，影响氧化率的最高显著因素是温度，其次是ｐＨ，接触时间等，臭氧很容易氧化腐植酸，在３０℃，ｐＨ９．０～１０．０，７ｍｉｎ内，ＣＯＤ去除率可达６０％以上，对邯郸热电厂生产处理也取得良好效果，３５℃，ｐＨ７．４～７．６，１０ｍｉｎ内，ＣＯＤ去除率可达６７％，可望将臭氧化水处理工艺应用于电厂水处理。     

Crystallization behavior of poly(N‐methyldodecano‐12‐lactam). IV. Nonisothermal crystallization

Nonisothermal crystallization of poly(N‐methyldodecano‐12‐lactam) (MPA) was investigated using DSC method at cooling rates of 2–40 K/min. With increasing cooling rate, crystallization exotherms decreased in magnitude and shifted toward lower temperatures. Subsequent heating runs (10 K/min) showed an exotherm just above T_g, which increased in magnitude with the rate of preceding cooling run, corresponding to the continuation of primary crystallization interrupted as the system crossed T_g on cooling. Kinetic evaluation by the Avrami method gave values of exponent n close to 2.0, suggesting two‐dimensional crystal growth combined with heterogeneous nucleation. The Tobin method, covering the intermediate range of relative crystallinities, provided n ? 2.20, suggesting possible partial involvement of homogeneous nucleation at later stages of nonisothermal crystallization. The crystallization rate parameter k^1/n showed a linear dependency on cooling rate for both methods, the Tobin values being slightly higher. The Ozawa approach failed to provide reasonable values of the kinetic exponent m of MPA. The Augis–Bennet method was used to determine the effective activation energy of the entire nonisothermal crystallization process of MPA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 564–572, 2005     

加盐微乳洗涤剂洗涤过程研究

微乳浸泡型洗涤剂较有机溶剂更节能、安全、环保.在微乳液洗涤剂中加入少量无机盐能明显改善洗涤效果.在m(SDS)∶ m(C10H22)∶m(C4H9OH)∶ m(H2O)=112∶96∶75∶178的微乳液中加入总质量0.1%的NaCl,此微乳液洗涤剂对原油洗涤过程的速率方程为一级,洗涤过程活化能为27.77 kJ·mol-1,比无盐微乳液洗涤剂低6.24 kJ·mol-1.25℃下,被原油污染的布样置于加盐微乳液中浸泡360 min,洗净度可达90.91%,比无盐徽乳液洗净度高5.45%.低温段加盐微乳液洗涤效果好于无盐微乳液,温度升高后,随洗涤时间的延长,加盐微乳液的洗涤效果不如无盐微乳液.     

Quick Activation of Optimized Zeolites with Microwave Heating and Utilization of Zeolites for Reusable Desiccant

Effectiveness of microwave heating in an activation treatment of zeolites was studied and utilization of zeolites for reusable desiccant was examined. X zeolite was chosen as a target material for its large adsorption capacity. Na-X zeolite easily caused a thermal runaway by microwave radiation of 500 W but Ca contained X zeolite merely reached ca. 573 K under the same conditions. Mixtures of Na-X and Ca-X with suitably mixed ratios did not cause the thermal runaway and their heating temperatures were controlled (>573 K) at will. Under the most suitable conditions, the mixture reached a dehydration degree of 92%. A degradation degree of adsorptive capacity of the mixture for water was examined after three treatments. The average degradation degree was 1.5% per treatment. The heating method is promising as a quick and easy technique to activate zeolite. By applying the method, the zeolites with suitable mixing ratios are usable as a reusable desiccant for home use.     

Fischer–Tropsch synthesis. Compositional changes in an iron catalyst during activation and use

The equilibrium phase compositions of iron have been calculated for gas compositions that could be encountered during the Fischer–Tropsch synthesis. The gas compositions measured experimentally for CO conversion levels in the 30–90% range show that iron should be present as the carbide phase. However, experimental characterization of iron catalysts show that a significant fraction of the iron is present as Fe₃O₄ following synthesis for several days. A model that can account for the experimental catalyst phase composition and the gases present in the reactor would have a core of Fe₃O₄ and an outer layer of iron carbides.     

抗氧剂3114合成反应热力学和动力学的研究

研究了常温溶剂法合成抗氧剂3114反应热力学和动力学过程。控制温度在117±2℃,研究结果表明,反应是零级反应,反应速率常数k=1.91×10-3/min,反应的平衡常数K=138.4(mol/L)-6,反应活化能Ea=1366.2J/mol。     

Degradation of acrylonitrile–ammonium itaconate copolymers

Acrylonitrile–ammonium itaconate copolymers were prepared by H₂O/dimethyl formamide suspension polymerization technique. Differential scanning calorimetry results of the degradation of acrylonitrile–ammonium itaconate copolymers in air are presented. The apparent activation energy of degradation of the copolymer was calculated using the Kissinger method. Effects of copolymerization conditions on the apparent activation energy of copolymer were studied. Increasing the dimethyl formamide concentration in the solvent mixture leads to a rapid increase in the degradation apparent activation energy of acrylonitrile–ammonium itaconate copolymer. The value of the degradation apparent activation energy of the copolymer synthesized in dimethyl formamide solvent increases up to 168.3 kJ mol^?1. The apparent activation energy decreases quickly along with an increase in ammonium itaconate concentration, and this change becomes less prominent as the weight ratio of ammonium itaconate/acrylonitrile goes beyond 6/94, ΔE_a = 89.4 ± 2.0 kJ mol^?1. The apparent activation energy shows a trend of increase with increasing copolymerization temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1708–1711, 2005     

Role of primary and secondary protein structure in neurotransmitter receptor activation mechanisms

A proton transfer triggered by a ligand interacting with thereceptor had been suggested as the initial step in the activationof a receptor for the neurotransmitter serotonin (5-hydroxy-tryptamine;5-HT). To evaluate the role of the receptor macromolecule inmodulating the primary molecular event in ligand-mediated activation,the process of proton transfer was analysed in the environmentof a protein model for the 5-HT receptor. In the absence ofa detailed receptor structure, the enzyme actinidin was chosenas the model for the receptor based on criteria obtained fromstructure-activity considerations on the ligands. The firstsimulation of a mechanism for receptor activation was performedon this model using methods of theoretical chemistry to studythe effect of specific structural elements. The premise is thatthe role of the elements of secondary structure of soluble proteins(e.g. actinidin) in determining structure-function relationsin these macromolecules is maintained when these elements arepart of membrane-bound receptor proteins. Results from the calculationsof the effects of the six alpha helices of actinidin on theproton transfer process from the imidazolium side chain of His162 to the thiol side chain of Cys 25 in the protein show thatthe helices contribute in different ways to modulate the energyof proton transfer. The largest helix, Al, opposes the protontransfer through the effect of the helix dipole. The chargedresidues (primary structure) in helix A3 favor the proton transfer,and mask the effect of its helix dipole (secondary structure)which opposes the transfer. The direction of the proton transfersimulated for the activation mechanism is opposite to that assumedin the catalytic process of the thiol protease, and the entireprotein environment opposes the transfer. This supports thespecific role of the ligand in triggering the proton transferas a response to its binding.     

阴离子型微乳洗涤剂洗涤过程动力学研究

采用微乳手段，将十二烷基硫酸钠(SDS)、癸烷、正丁醇与水制成微乳液。当m(SDS)：m(C10H22)：m(C4H9OH)：m(H2O)=112：96：75：178时形成的微乳液对棉布上由原油形成的污垢的洗涤过程的速率方程为一级，洗涤过程活化能为13．2kJ／mol。30℃浸泡4h洗净度为88％，比用含相同质量分数的表面活性剂溶液的洗涤效果高出37％。