聚合物载体－稀土金属络合物的研究 ⅩⅢ．聚［苯乙烯－甲基丙烯酸β（甲基亚硫酰基）乙酯］的结构与其稀土金属络合物催化丁二烯聚合的活性

从测得的竞聚率计算了单体链节在聚［苯乙烯－甲基丙烯酸β（甲基亚硫酰基）乙酯］（ＰＳＭ）中的序列分布。苯乙烯（Ｓ）或甲基丙烯酸β（甲基亚硫酰基）乙酯（Ｍ）的长序列的概率随着ＰＳＭ中相应单体含量的增加而增加。对于Ｓ和Ｍ摩尔分数大致相等的ＰＳＭ，单体链节的长序列分布函数值相接近。用与此结构相近的ＰＳＭ合成的稀土金属络合物，其催化活性不佳。在Ｍ短序列分布和Ｓ长序列分布较高的情况下，络合物的催化活性最好。所得聚丁二烯的微观结构与ＰＳＭ中单体单元的分布无关。     

Nitric oxide reduction and carbon monoxide oxidation over carbon-supported copper-chromium catalysts

Carbon supported copper-chromium catalysts are shown to be very active for both the reduction of nitric oxide with carbon monoxide and the oxidation of carbon monoxide with oxygen. Mixed copper-chromium oxide active phases have good activity in the simultaneous removal of nitric oxide and carbon monoxide from exhaust gases. The influence of several catalyst variables has been investigated. The activity per volume of catalyst increases with increasing loading, while the intrinsic activity shows a maximum around C/M=100−50. An optimum catalyst for nitric oxide reduction and carbon monoxide oxidation has a copper/chromium ratio of 2/1. The apparent activation energy for the carbon monoxide oxidation over carbon supported copper-chromium catalysts is 77 kJ/mol, suggesting that the Cu---O bond rupture is the rate-limiting process. The reduction of nitric oxide takes place at higher temperatures. Since all catalysts have a low selectivity for molecular nitrogen formation at lower temperatures, the dissociation of nitric oxide is probably rate determining, resulting in a slightly reduced catalyst system. In an excess of carbon monoxide the reaction is first-order in nitric oxide and zero-order in carbon monoxide. Moisture inhibits the reaction by reversible competitive adsorption, whereas carbon dioxide does not. Oxygen completely inhibits the reduction of nitric oxide due to the more rapid reoxidation of the catalytic sites compared to nitric oxide. Therefore, the reduction of nitric oxide takes place only when all oxygen has been converted and, hence, is shifted to higher temperatures. As a possible consequence, the production of nitrous oxide is reduced. Nitric oxide and molecular oxygen react preferentially with carbon monoxide, so, in an excess of oxidizing component, gasification of the carbon support occurs at higher temperatures after carbon monoxide has been completely consumed.     

Unperturbed dimension of poly(4-acetoxystyrene) measured in good and theta solvents

In order to obtain the additional data concerning the unperturbed dimension of poly-4-substituted styrene, light scattering measurements are performed on the twenty-two fractions with molecular weight of (0.91–352)·10⁴ of poly(4-acetoxystyrene) in dioxan at 25°C, from which the molecular weight obtained was found easily to be evaluated with the gel permeation chromatography using THF. Phase separation experiments for this polymer indicate that the theta state is attained in isopropyl acetate at 19.7°C and butyl acetate at 26.8°C. By making viscosity measurements at that state, the value of K_Θ is directly evaluated as 5.4·10^?4 dl g^?1. The limiting viscosity number is also obtained in good solvents, THF and dioxan, at 25°C and constants of the Mark-Houwink-Sakurada equation in each solvent are determined. Further, approximately the same K_Θ as above is obtained from these data with the Stockmayer-Fixman plot. The calculated value of steric factor, 2.37, on this polymer may be plausible, compared with those of polyvinylaromatic derivatives.     

中变催化剂失活典型事例剖析

通过2起中变催化剂失活的事件，从理论上剖析其根源，并探讨防范的对策。     

沸石加氢处理催化剂的制备方法

考察了渣油加氢处理催化剂制备过程中引入一种低硅铝比沸石的情况，它不仅提高催化剂的酸性，而且由于引入的分子筛孔径集中，最终使催化剂具有集中的孔分布，弥补了制备高活性催化剂采用混捏法的不足，制备出来的催化剂性能更优异。     

合成直链烷基苯的锆磷铝固体酸催化剂 I.催化剂合成及其影响因素

合成了一系列用于苯与直链烯烃烷基化反应的含有杂原子的磷铝分子筛固体酸催化剂 (MeZrAPO 5 ) ,同晶取代磷铝分子筛骨架中磷和铝的杂原子包括锆和至少一种选自硅、硼、镓、锗、铁、镁、锡等的元素。考察了晶化温度、晶化时间、杂原子种类、铝源等因素对催化剂合成的影响 ,探索了合成样品中模板剂脱除的最佳条件。结果表明 ,晶化温度高于 15 0℃、n(TEA) /n(Al2 O3 )≥ 1 5以及加入Zr原子都有利于直接生成MeZrAPO 5晶相 ;用小晶粒和高结晶度的铝源合成时 ,分子筛的结晶度高。     

合成吡啶类化合物用催化剂的再生行为研究

对合成吡啶类化合物用的失活催化剂上的结焦物进行了元素分析 ,并着重对失活催化剂的再生行为进行了研究。得到了不同失活程度催化剂的再生曲线及相同失活程度、不同再生条件下的再生曲线。经回归求得了一简单的再生反应动力学经验方程式 ,其中反应级数为碳含量的 1.16 5级 ,活化能为 4 2 .5 72kJ/mol,计算值与实验值的平均相对误差为 6 .5 %。     

医用聚氯乙烯材料的表面光接枝改性

研究了在不排氧氛围下 ,紫外光照射 ,以二苯甲酮 (BP)为光引发剂 ,甲基丙烯酸缩水甘油酯(GMA)在医用聚氯乙烯 (PVC)薄膜表面的气相接枝聚合。探讨了反应条件对接枝结果的影响 ,并用正交法指出了影响因素的显著性。用傅立叶红外 (FT- IR)、水接触角作为接枝改性结果的表征。FT- IR谱图表明 GMA已接枝到 PVC膜表面。水接触角由接枝前的 78°下降到 5 4°     

探讨缩聚催化剂对聚酯切片质量的影响

通过试验，分析比较了江西Sb2O3、南宁Sb2O3和大连Sb(Ac)3三种缩聚催化剂对聚酯切片质量的影响。试验结果表明，Sb(Ac)3是优良的缩聚催化剂。     

Object-oriented DBMS requirements

The requirements on an object-oriented DBMS for management of information in a large, complex enterprise are presented. These requirements aid in the achievement of an environment characterized by data sharing, open architectures, application and data portability, and assurance of data integrity. They were defined from the point of view of a user of the DBMS; therefore they describe the expected functionality of the DBMS and do not specify the method of implementation to achieve this functionality. They encompass requirements on the data model, query and data manipulation languages, the system architecure, interfaces to the system, change management, and transaction management.