Hydrogen production on iron–magnesium oxide in the high-temperature water-gas shift reaction

The effect of the structure of the achiral primary amine additive on the enantioselective heterogeneous catalytic hydrogenation of (E)-2-methyl-2-butenoic acid over cinchonidine modified Pd/Al₂O₃ was studied. It was found that a variety of amines increase the enantioselectivity, which was always accompanied by decrease in the initial rate of the hydrogenations. Based on these results, the participation of the amine additive in the formation of the intermediate complex responsible for enantioselection was suggested. A decrease in the reaction temperature resulted in further increase in the optical purity of the product up to 67%, the highest value reported in the hydrogenation of unsaturated aliphatic acids in this heterogeneous catalytic system so far.     

Synthesis of original para‐sulfonic acid aminoethylthioethylbenzenesulfonic by telomerization,and its grafting onto poly(VDF‐co‐HFP) copolymers for proton exchange membrane for fuel cell

The synthesis of a novel aromatic sulfonic acid bearing an amino function H₂N? C₂H₄? S? C₂H₄? C₆H₄? SO₃Na ( 1 ) from the radical addition of mercaptoethylamine hydrochloride onto styrene sodium sulfonate, and its subsequent grafting onto poly(vinylidene fluoride‐co‐hexafluoropropylene), poly(VDF‐co‐HFP), copolymer are presented. First, the radical telomerization, carried out under radical conditions and in water, led to various products [monoadduct ( 1 ), multiadducts, and polymers], the amounts of which depend on the experimental conditions and [mercaptan]₀/[monomer]₀ initial molar ratio (R₀). An R₀ ≥ 1 led to the monoadduct ( 1 ) only and achieved in ～85% yield. The zwitterionic isomer was obtained mainly and its chemical modification was possible to get an original aromatic sodium sulfonate containing an amino end group. A kinetic study of the telomerization was presented for R₀ < 1. Thermogravimetric analysis of the telomer showed that this compound was stable up to 200 °C. Second, the grafting of ( 1 ) onto poly(VDF‐co‐HFP) copolymer was also investigated. Such a grafting proceeded as expected by a classic mechanism of grafting of amines. Molar percentages of grafted telomer were assessed by ¹H NMR spectroscopy and by elemental analysis. Ion exchange capacity (IEC) values of the membranes were deduced from the mol % grafted telomer. Scanning electron microscopy pictures showed a good homogeneity in the cross‐section of membranes, and energy dispersive X‐ray evidenced that all SO₃Na groups of the grafted amine were changed into SO₃H after treatment with concentrated HCl. Method involving an impedance analyzer, working at increasing high frequencies was used to assess the protonic conductivities, σ. These values were lower than that of Nafion117^®, but σ increased with the IEC to 0.4 mS/cm at room temperature and 95% relative humidity. Water and methanol uptakes were also assessed, and it was shown that σ increased when water uptakes increased. Membranes started to decompose from 170 °C under air. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 121–136, 2009     

Anionic polymerization of methyl methacrylate by initiating systems based on lithium amides of various secondary amines

The anionic polymerization of methyl methacrylate in toluene at −78 °C with lithium amides of various secondary amines (diisopropylamine, N‐isopropylaniline, N‐n‐butylaniline, indoline, and N‐ethyl‐o‐toluidine) as initiators was studied. The tacticity of the resulting poly(methyl methacrylate)s (PMMAs) was dependent on the kind of secondary amine, and highly isotactic PMMAs (91–93% mm) were obtained when lithium amides of N‐isopropylaniline and N‐n‐butylaniline were employed. The isotacticity of the PMMAs further increased up to 98% mm with initiating systems composed of the lithium amides, n‐butyllithium, and transition‐metal halides (WCl₆, MoCl₅, and NbCl₅). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4405–4411, 2005     

新型桥连双锌配合物的合成和结构

合成了二(2-苯并咪唑亚甲基)胺及其副产物[2,5-二(苯并咪唑亚甲基)环二肽 ]的混合配体与助Zn(Ⅱ)的双核超氧化物歧化酶模型化合物．进行了元素分析、紫 外和红外表征;对配合物采用X射线衍射方法测定了晶体结构,并采用G94W程序对 副产物[2,5—二(苯并咪唑亚甲基)环二肽]进行了量子化学计算．     

新的离子型光敏聚酰亚胺

合成了新的复合光敏聚酰胺酸季铵盐,研究了光敏剂、交联剂以及化学结构对感光度的影响,并考察了其热稳定性。结果表明以3,3′,4,4′－联苯四酸二酐－间苯二胺为主链的聚酰胺酸合成的光敏聚酰胺酸季铵盐有较高的感光度,光敏剂米氏酮的含量在3－5％,交联剂2,6－双（4－叠氨苄基）－4－甲基环己酮的含量在8－10％为宜;光敏性叔胺二甲氨基乙醇肉桂叉乙酸酯的含量不可超过8％;由这种复合季铵盐合成的新的光敏聚酰胺酸盐在较低的温度200℃以下就可以完全酰亚胺化,但接近550℃才达到理论失重量。     

1—硫代—1磷杂—2，6，7—三氧杂双环[2,2,2]亲烷—4—甲撑烷氧基硫代磷酰胺的合成

以三氯硫磷、高位阻醇A等为材料,通过三步反应合成了化合物1－硫代－1磷杂－2,6,7－三氧杂双环[2,2,2]亲烷－4－甲撑烷氧基硫代磷酰胺。研究了化合物的^31P NMR和MSo产物的结构经元素分析和核磁共振等证实。     

Synthesis of Sterically Hindered Heteroaromatic Ketones under Phase-transfer and Metal-complex Catalysis Conditions. (Review)

We have correlated data on methods for obtaining sterically hindered ketones, derivatives of furan, thiophene, pyrrole, and pyridine. We examine routes to arylation of chroman-4-ones and synthesis of sterically hindered unsaturated and silicon-containing heteroaromatic ketones.     

环氧树脂体系固化反应及其复合材料介电性能

环氧树脂是一类综合性能优异的热固性高分子材料,作为胶粘剂、复合材料用树脂基体、涂料等形式广泛应用于电子电气、机械制造、化工防腐、航空航天等众多领域中,成为各工业领域中不可缺少的基础材料。本文综述了本研究室在咪唑／环氧树脂体系,稀土有机化合物、叔胺羧酸复盐／酸酐／环氧树脂体系,氰酸酯／环氧树脂体系,硼胺络合物／环氧树脂体系的固化反应机理、固化反应动力学及其固化物结构与性能关系,纤维含量、排列方向、偶联剂种类等对玻璃纤维增强环氧树脂基复合材料及其界面介电性能的影响等6个方面的研究进展。     

三氯乙酸酯与二级胺反应的研究

三氯乙酸酯与二级胺反应,在不同条件下得到不同的产物。当三氯乙酸酯与环状二级胺反应时,碳碳键断裂并生成胺基甲酸酯;而与链状二级胺反应时则发生碳氧键断裂并生成叔胺。