Hydrosilylation and dehydrocondensation reactions of methylhydridesiloxane to acrylic and methacrylic acids

The hydrosilylation of α,ω‐bis(trimethylsiloxy) methylhydridesiloxane (degree of polymerization ≈ 53) with acrylic and methacrylic acid with various ratios of the initial compounds, in the presence of platinum hydrochloric acid, has been investigated. In the presence of platinum hydrochloric acid, competitive dehydrocondensation reactions take place with the formation of various oligomers with various chemical links. In the later stages of the reaction, three‐dimensional systems have been obtained. During dehydrocondensation, the reaction order, reaction rate constants, and activation energy have been determined. The structures of the synthesized oligomers have been determined with IR and NMR spectroscopy data. Gel permeation chromatography, differential scanning calorimetry, and X‐ray analyses of the synthesized oligomers have been carried out. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3243–3252, 2007     

萘降解菌的筛选及降解性能的初步研究

微生物降解是多环芳烃从土壤和水环境中消失的主要途径。本文从加油站废油排放口附近被污染土壤中筛选到两种降解萘的混合菌H1、H2并从中分离出一株纯菌C_1。研究发现,利用纯无机盐培养基加萘作为唯一碳源要比加入其它营养物质的培养基对于筛选萘降解菌更为有利。H_1、H_2和C_1均能以萘为唯一碳源生长,在萘初始浓度为1000mg/L的纯无机盐培养基中培养40h后,培养液中微生物数量分别增长10倍以上,利用气相色谱测得萘的降解率都达到99．6％以上。     

中药降香对酪氨酸酶激活作用的动力学研究

酪氨酸酶是生物合成黑素的主要酶。降香有促进酪氨酸酶活性的作用。通过对中药降香的水提取液和乙醇提取液促进酪氨酸酶活性作用的观察研究及降香提高酪氨酸酶活性的动力学观察研究，得到Lineweaver-Burk曲线、动力学回归方程及米氏常数Km值。为研究中药有效成分激活黑素细胞的机理奠定了基础。     

Continuous emulsion polymerization of vinyl acetate. II Operation in a single Couette–Taylor vortex flow reactor using sodium lauryl sulfate as emulsifier

Continuous emulsion polymerizations of vinyl acetate were conducted at 50°C in a single continuous Couette–Taylor vortex flow reactor (CCTVFR) using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator. The polymerization can be carried out very smoothly and stably, but the steady‐state monomer conversion attained in a CCTVFR is not as high as that in a plug flow reactor (PFR), but only slightly higher than that in a continuous stirred tank reactor (CSTR), even if the Taylor number is adjusted to an optimum value. Also, the effects of operating variables, such as the emulsifier, initiator, and monomer concentrations in the feed and the mean residence time on the kinetic behaviors were almost the same as those observed in a CSTR. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2755–2762, 2002     

Elucidation of the miniemulsion stabilization mechanism and polymerization kinetics

Styrene/hexadecane miniemulsions were polymerized at 50°C using a redox initiator. The miniemulsions and their corresponding latexes were characterized in terms of size, polymerization rate, and surface properties. The resulting data were analyzed to elucidate the miniemulsion stabilization and polymerization mechanisms. It was found that the free surfactant concentration exceeded the critical micelle concentration when large amounts of surfactant (60 mM sodium lauryl sulfate) were used, resulting in simultaneous micellar and droplet nucleation. Most surfactant was on the surface of the droplets (85%) or particles (95%). The fractional surface coverage was proportional to the surfactant concentration to the 0.55 power. Using a particle diameter equation, the number of particles was calculated to be proportional to the surfactant concentration to the 1.35 power. Through direct particle size measurements, a power of 1.38 was confirmed. The rate of polymerization was determined by reaction calorimetry to be proportional to the number of particles to the 0.59 power, in contrast to classical Smith–Ewart kinetics for conventional emulsions (1.0 power). The average number of radicals per particle was estimated from the rate and number data, and varied with the particle diameter to the 0.97 power. The observed kinetic dependencies were validated through an extension of Smith–Ewart theory. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3987–3993, 2003     

DIFFUSION AND REACTION OF BENZENE HYDROGENATION OVER POROUS Ni/γ-Al_2O_3 CATALYST

The macro-kinetics of benzene hydrogenation over porous Ni/γ-Al_2O_3 catalyst was measured with asingle-pellet diffusion reactor.Based on the dusty-gas model,the differential equations by taking into account ofthe variation of effective diffusivities with the composition were derived to describe the diffusion and reactionprocesses of reacting species over porous catalyst.Using the tortuosity factors determined under the condition ofsteady physical diffusion,the global reaction rates were calculated by solving the equations,and the results are ingood agreement with the experimental data obtained.     

溶剂对维生素C单晶生长动力学的影响

引　言当过饱和溶液中产生晶核或加入晶种时 ,溶质分子在过饱和度的推动下使晶核或晶种长大的过程就是晶体生长 .晶体生长动力学决定了晶体产品的形态及其物理性质 ,是结晶过程设计、优化和操作的基础 ,在结晶过程研究中占有重要地位[1,2 ] .晶体生长的外部条件例如过饱和度、温度、溶剂等都直接影响到晶面吸附情况的变化、晶体比表面自由焓 ,从而影响晶面的生长速度[3,4 ] .单晶研究是借助于显微镜、照相机、衍射仪等观察手段测定单晶各方向的尺寸随时间的变化 ,确定晶体生长动力学的方法[5] .作者曾采用间歇动态法实验测试维生素C在水 乙…     

邻羟基环己基丙烯酸酯光聚合动力学研究

采用实时红外光谱技术(RTIR)研究了邻羟基环己基丙烯酸酯(HCA)光聚合反应动力学,探讨了光照强度、光引发剂种类和浓度对其光聚合动力学的影响,并与脂肪族羟基丙烯酸酯单体丙烯酸羟乙酯(HEA)进行了对比。结果表明,最终双键转化率和相对反应速率随光强增大而增加;光引发剂浓度对最终双键转化率和反应速率的影响随引发剂不同呈现不同规律;与HEA相比,HCA具有更高的反应活性,但最终双键转化率较低。     

烯（醚）醛一步法合成异戊二烯技术开发—基础理论研究进展

本文介绍了烯(醚)醛一步法合成异戊二烯技术开发中,基础理论研究工作的进展,其中包括化学热力学、化学动力学、再生烧炭本征动力学和扩散动力学等理论研究。并针对该反应特征进行了化学反应规律和流动传递规律的研究。建立了流化床反应器数模和流化床再生器数模,为工程技术开发提供理论依据。     

Study of the composition effect of glass ceramic and silver on poly(vinyl butyral) thermal degradation with thermogravimetric analysis

The thermal degradation of poly(vinyl butyral) (PVB)/glass ceramic, PVB/Ag, and PVB/glass ceramic/Ag composites was investigated with thermogravimetric analysis in nitrogen and air. Thermogravimetric data revealed that the compositions of both inorganic materials in air could greatly influence the thermal degradation of PVB. The degradation reactions of PVB/ceramic and PVB/Ag composites began earlier and accelerated rapidly at lower temperatures. The overall degradation period was obviously shortened for the thermal degradation of PVB/Ag in air, whereas a longer time was required for the PVB/ceramic composite than for PVB. Moreover, dual effects of ceramic and Ag on the thermal degradation of PVB were observed for PVB/ceramic/Ag composites. In addition, the catalytic effects of ceramic and Ag on the degradation reaction of PVB in air were verified with a kinetic analysis. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2142–2149, 2004