Effect of excess halide on the palladium‐catalyzed insertion‐triggered radical copolymerization of methyl acrylate and 1‐hexene

[Pd₂(μ‐Cl)₂(C₆F₅)₂(tht)₂] ( 1 ) is a very efficient initiator of the radical polymerization of methyl acrylate, but it is not active in the polymerization of methyl methacrylate or in the copolymerization with 1‐hexene. The addition of an excess of NBu₄Cl to solutions of [Pd₂(μ‐Cl)₂(C₆F₅)₂(tht)₂] ( 1 ) provides an initiator system that copolymerizes methyl acrylate and 1‐hexene by an insertion‐triggered radical mechanism. Random copolymers are obtained with 11% incorporation of 1‐hexene in moderate yields (about 35%). Studies of the decomposition products obtained after the first insertion of methyl acrylate in the Pd? C₆F₅ bond of 1 show that the addition of excess halide in the presence of monomer favors the homolytic cleavage of the Pd? C bond, and the generation of the radicals that are active species in the polymerization, versus alternative evolution pathways. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5682–5691, 2006     

Metallocene copolymers of propene and 1‐hexene: The influence of the comonomer content and thermal history on the structure and mechanical properties

The relationships between the structure and properties have been established for copolymers of propylene and 1‐hexene synthesized with an isotactic metallocene catalyst system. The most important factor affecting the structure and properties of these copolymers is the comonomer content. The thermal treatment, that is, the rate of cooling from the melt, is also important. These factors affect the thermal properties, the degree of crystallinity, and therefore the structural parameters and the viscoelastic behavior. A slow cooling from the melt favors the formation of the γ phase instead of the α modification. Regarding the viscoelastic behavior, the β relaxation, associated with the glass‐transition temperature, is shifted to lower temperatures and its intensity is increased as the 1‐hexene content raises. The microhardness values are correlated with those of the storage modulus deduced from dynamic mechanical thermal analysis curves, and good linear relations have been obtained between these parameters. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1253–1267, 2006     

Theoretical Analysis of the Motional Model of Nonlinear Heterogeneous Catalysis

In this paper, a model of the motional nonlinear heterogeneous catalysis process is discussed using the characteristic line method, the analytical results of elution profile are obtained and the formula which determines the parameters of reaction rate and adsorption isotherm through the motional measurement data under the nonlinear condition is given.     

La对选择性加氢催化剂Co/γ-Al2O3的改性研究

应用XPS、DTG、DTA和XRD技术，分析了La提高催化剂Co-La／γ-Al2O3活性的原因．加入La后，XPS分析得出，Co2p在催化剂表层含量是未加前的1．65倍；DTG和DTA表征显示，La对催化剂的热效应影响很小；XRD分析表明，La的加入提高了Co3O4的分散度．     

负载型双金属簇催化剂的多相一氧化碳加氢反应性能

负载型双金属簇催化剂的多相一氧化碳加氢反应性能索全伶，李晔（内蒙古工业大学化学工程系，呼和浩特０１００６２）殷元骐，金道森（中国科学院兰州化学物理研究所，兰州７３００００）关键词一氧化碳加氢，多相催化，双金属簇催化剂，钾效应。１．引言异核金属羰基簇作...     

活性炭负载杂多酸催化剂的研究进展

介绍了以活性炭为载体的负载型杂多酸催化剂的研究进展,包括制备方法、影响负载量的因素、负载催化剂的性质、吸附模型和脱附作用。总结了杂多酸在活性炭上的吸附形态研究以及杂多酸与活性炭表面含氧基团的化学键合作用的研究成果,展望了该催化剂未来的研究方向。     

Fe/Zn双金属氰化物催化剂催化环氧丙烷聚合的活性结构研究

以氯化锌、铁氰化钾（含有整合剂）的水溶液为原料，合成了铁锌双金属氰化物（DMC）催化剂。为获得高活性的DMC催化剂，需将叔丁醇 、多元醇螯合剂螯合至其结构中，用XRD、XPS等分析手段，对铁锌DMC催化剂的结构与活性进行分析表征。实验发现，DMC催化剂的晶体结构与螯合剂密切相关，螯合剂能显著降低DMC催化剂的结晶程度，从而提高DMC催化剂的活性。同时，氯化锌过量也有利于DMC催化剂活性的提高。并表征了相关DMC催化剂的活性中心。     

Catalytic nitrobenzene oxidation of lignins

Alkaline nitrobenzene oxidation of hardwood and softwood lignins in the presence of redox and phase-transfer catalysts was studied. The selectivity of oxidation of lignins increased by 1.7 to 1.9 times. A possible mechanism of catalysis is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 3004–3007, December, 1996.     

A model of adsorption at liquid-solid interface involving association in the bulk phase

A model of monolayer adsorption of binary liquid mixtures on homogeneous and heterogeneous solid surfaces involving association of one component in the bulk phase is discussed. Suitable model calculations, illustrating association and heterogeneity effects, have been performed according to an equation derived for adsorption excess. This equation has been examined by using the experimental data of adsorption of alcohols from benzene andn-heptane on silica gel.

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Adsorptionsmodell für die Grenzfläche Feststoff-Flüssigkeit unter Berücksichtigung der Assoziation in der Flüssigkeitsphase

Zusammenfassung Es wird ein Adsorptionsmodell binärer, flüssiger Mischungen an homogenen und heterogenen Oberflächen von Feststoffen unter Beachtung der Assoziation eines der Bestandteile in der Flüssigkeitsphase diskutiert. Mit der aus dem Oberflächenüberschuß abgeleiteten Gleichung wurden entsprechende Modellberechnungen durchgeführt, die die mit Assoziation und Heterogenität verbundenen Effekte illustrieren. Die Gleichung wurde für die experimentellen Daten der Alkoholadsorption aus Benzol undn-Heptan an Kieselgel überprüft.

     

壳聚糖负载贵金属催化剂的研究进展

壳聚糖负载的贵金属催化剂显示了高催化活性和高选择性，已被用于氧化反应、氢化反应、烯丙基取代反应、羰基化反应、Suzuki和Heck偶联反应、烯烃的不对称二羟基化反应及有机醛、酮的合成反应体系中。本文对其制备方法、可能结构及其在各种反应体系中的催化性能进行了综述。