SYNTHESIS, CROSSLINKING MECHANISM AND PROPERTIES OF A POLYACRYLATE/POLYURETHANE COMPOSITE COATING

A polyacrylate/polyurethane (P(A) / P(U)) composite coating has been prepared bycrosslinking an acetoacetylated polyacrylate with a vinylic group terminated polyurethaneat room temperature. A model Michael reaction between ethyl acetoacetate (EAA) andmethyl acrylate (MA) was designed to study the crosslinking mechanism. It was foundthat the two active hydrogen atoms in acetoacetyl group can both add to vinylic groupsand the yield of mono- and bis-adducts are much affected by the molar ratio of acetoacetylto vinylic groups. Higher crosslinking degree and better properties could be obtained withdecreasing the molar ratio of the two active groups from 1/1 to 0.6/1 in the compositecoatings.     

过硫酸盐和N,N,N′,N′-四甲基乙二胺体系引发烯类聚合机理的研究

<正> 过硫酸盐和N,N,N′,N′-四甲基乙二胺(TMEDA)体系用作烯类聚合的引发剂已有报道。本文报道该引发体系的反应机理。1.实验方法     

A Kinetic Evidence for the Nitroxyl Radicals Recycling Mechanism in the Photostabilizing Process of HALS

The photoinduced bulk polymerization of a reactive-hindered amine fight stabilizers(r-HALS), 4-acryloyl-2, 2, 6, 6-tetramethylpiperidinyl (ATMP), was performed at 80℃ by using a DPC technique. An unique periodic exponential attenuation-type oscillating curve was found when the polymerization was carried out in air, but this phenomenon was not found in nitrogen.It is supposed that this unique kinetic performance may be attributed to nitroxyl radicals that are produced in situ from the oxidation of ATMP. ATMP polymer with narrow polydispersity (d =1.03) can be obtained by photoinduced solution polymerization of ATMP. The signal detected in ESR may be assigned to the nitroxyl radicals in the matrix of ATMP polymer. Since this kind of recycling of nitroxyl radicals is well documented for the photostabilizing mechanism of HALS, the present results may serve as a kinetic evidence for this mechanism.     

锌-硫氰酸盐-孔雀绿体系溶剂浮选机理及影响因素的探讨

本文通过对锌(Ⅱ)—硫氰酸盐—孔雀绿体系溶剂浮选过程的考察,提出了待测Zn~(2+)离子从水相被输送到有机相,可以用吸附机理和粘附机理来解释;同时还对影响锌溶剂浮选的主要因素:溶液的pH,气泡的大小和气体流速等进行了讨论。     

Highly efficient redox isomerization of allylic alcohols at ambient temperature catalyzed by novel ruthenium-cyclopentadienyl complexes--new insight into the mechanism

A range of ruthenium cyclopentadienyl (Cp) complexes have been prepared and used for isomerization of allylic alcohols to the corresponding saturated carbonyl compounds. Complexes bearing CO ligands show higher activity than those with PPh3 ligands. The isomerization rate is highly affected by the substituents on the Cp ring. Tetra(phenyl)methyl-substituted catalysts rapidly isomerize allylic alcohols under very mild reaction conditions (ambient temperature) with short reaction times. Substituted allylic alcohols have been isomerized by employing Ru-Cp complexes. A study of the isomerization catalyzed by [Ru(Ph5Cp)(CO)2H] (14) indicates that the isomerization catalyzed by ruthenium hydrides partly follows a different mechanism than that of ruthenium halides activated by KOtBu. Furthermore, the lack of ketone exchange when the isomerization was performed in the presence of an unsaturated ketone (1 equiv), different from that obtained by dehydrogenation of the starting allylic alcohol, supports a mechanism in which the isomerization takes place within the coordination sphere of the ruthenium catalyst.     

超临界状态下炭基材料的储氢

评介了目前各种储氢方法，指出了炭基材料作为储氢材料的优势，综述了近年来纳米炭材料在储氢方面的进展，详细探讨了超临界状态下氢气在纳米孔隙中的吸附机理，并在此基础上提出了研究中的问题及进一步的研究方向。     

Pulse radiolysis study of I− oxidation with radical anions Cl2 ⋅− in an aqueous solution

Radiation-chemical transformations of chloride solutions in the presence of iodide additives were studied by pulse radiolysis. Radical anion Cl₂ ^⋅− oxidize I⁻ ion, while in the secondary reactions Cl₂ reacts with I⁻ to form a mixed trihalide ion ICl₂ ⁻. A reaction model that satisfactorily describes the experimental data was proposed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1336–1340, June, 2005.     

橡胶增韧环氧树脂机理的研究

本文研究了固化剂种类、环氧基体平均网链长度和分散相与基体间键合情况对体系韧性等的影响.结果说明,基体平均网链长度是一个更为重要的影响因素.分散相与基体间的化学键合也是重要的.文中对橡胶增韧环氧树脂的机理提出了见解.在交联密度较低的材料中,在橡胶颗粒附近叠加的应力场诱发下发生纵深度较大的断裂过程.分散相与基体间的化学键合增大该应力场强度有利于加大断裂过程区.     

H2CCF自由基与HNCO反应机理的理论研究

采用密度泛函理论的B3LYP方法, 在6-311＋＋G(d,p)基组水平上研究了H₂CCF自由基与HNCO的微观反应机理, 优化了反应过程中的反应物、中间体、过渡态和产物, 为了获得更精确的能量信息, 还在QCISD(T)/6-311＋＋G(d,p)基组水平上计算了各物质的能量．振动分析结果和IRC分析结果证实了中间体和过渡态的真实性, 计算所得的成键临界点电荷密度的变化也确认了反应过程．对于H₂CCF自由基与HNCO反应, 我们找到了六条可行的反应通道, 结果分析表明通道H₂CCF＋HNCO→IM3→TS5→H₂CCFH＋NCO控制步骤活化能最低, 是该反应的主要通道, 在此反应过程中有稳定的氢键复合物IM3生成, 还表现出氢原子迁移的反应特征．     

Theoretical study of ribonucleotide reductase mechanism-based inhibition by 2'-azido-2'-deoxyribonucleoside 5'-diphosphates

2'-azido-2'-deoxyribonucleoside 5'-diphosphates are mechanism-based inhibitors of Ribonucleotide Reductase. Considerable effort has been made to elucidate their mechanism of inhibition, which is still controversial and not fully understood. Previous studies have detected the formation of a radical intermediate when the inhibitors interact with the enzyme, and several authors have proposed possible structures for this radical. We have conducted a theoretical study of the possible reactions involved, which allowed us to identify the structure of the new radical among the several proposals. A new reactional path is also proposed that is the most kinetically favored to yield this radical and ultimately inactivate the enzyme. The energetic involved in this mechanism, both for radical formation and radical decay, as well as the calculated Hyperfine Coupling Constants for the radical intermediate, are in agreement with the correspondent experimental values. This mechanistic alternative is fully coherent with remaining experimental data.