Preparation and structural determination of siloxane-modified sulfone-containing epoxy resins

Siloxane-modified sulfone-containing epoxy resins (ESBS) were prepared by polycondensation of PMPS and/or PDMS siloxane oligomers with EBS, the sulfone-containing epoxy resin. Structures were analyzed by IR, ¹H-, and ¹³C-NMR. The siloxane content in the copolymers was determined by ¹H-NMR with an integration technique. Epoxy equivalent weight (EEW) determination indicated that the oxirane ring of EBS was intact with this hot-melt procedure. The GPC measurement of these ESBS copolymers showed that molecular weight (MW) increased with increasing siloxane content in PMPS-modified copolymers. Evidence of siloxane incorporation in the copolymer was discussed. © 1996 John Wiley & Sons, Inc.     

Synthesis of bis-ketene N,S-acetals with a polymethylene linkage

α-Aroyl substituted bis-ketene N,S-acetals 3–6 with a polymethylene linkage, N,N′-bis(1-methylthio-2-aroyl)vinyl polymethylene diamines, were synthesized by reactions between α-aroyl ketene dithioacetals 1 and polymethylene diamines 2 in moderate yields. © 1996 John Wiley & Sons, Inc.     

Oxidation of methanol catalyzed by silica-supported polystannazane–copper complex

Silica-supported polystannazane–copper complex has been prepared and used as a catalyst for the oxidation of methanol. The results showed that the catalyst could catalyze the oxidation of methanol to formaldehyde at a high yield and selectivity at 30°C and under 1 atm mild conditions. The N/Cu mole ratio in the complex, temperature and the amount of NaOH additive had much influence on the catalytic activity. The complex was stable during the reaction and could be used repeatedly.     

Preparation of palladium clusters protected by silica-supported,crosslinking, partially phosphorylated poly(vinyl alcohol) and their catalytic activity

The palladium cluster protected by silica-supported, crosslinking, partially phosphorylated poly(vinyl alcohol) (P-PVA) was prepared from a crosslinking P-PVA–Pd(II) complex by reduction in alcohol. The P-PVA–Pd complex and the palladium cluster protected by P-PVA were analyzed by electron spectroscopy, X-ray photoelectron spectrometry and transmission electron microscopy. The complex formation between the Pd(II) ion and phosphoric acid groups in P-PVA was important in the formation of a fine palladium cluster. Palladium clusters protected by silica-supported crosslinking P-PVA were used as catalysts for the hydrogenation of nitrobenzene or acrylic acid at 30°C under atmospheric pressure. The palladium cluster protected by crosslinking P-PVA supported on silica was the most active catalyst, was stable and had no by-products, compared with the palladium cluster protected by silica-supported noncrosslinking P-PVA or PVA.     

Catalytic hydrogenation of aromatic nitro compounds by non-noble metal complexes of chitosan

Silica-supported mono-metal (such as Ni, Cu) complexes and mixed metal (such as Cu/Zn, Cu/Cr) complexes of chitosan have been prepared. It is found that these non-noble metal complexes could be used as efficient catalysts for the hydrogenation of aromatic nitro compounds. The effects of type of metal, reaction temperature and pressure, solvent, nitrogen/metal molar ratio in the complex catalysts on the yields from nitrobenzene to aniline have been examined. It was also found that catalysts are active for the catalytic hydrogenation of other aromatic nitro compounds such as 2-nitroanisole, 2-nitroaniline, 2-nitrotoluene and 1-chloro-4-nitrobenzene.     

Epoxidation of styrene catalyzed by metal complexes of poly(vinylbenzyl)acetylacetonate

The epoxidation of styrene to styrene oxide at higher than 96% yield has been achieved by the catalysis by poly-(vinylbenzyl)acetylacetonate complexes of cobalt(II) or manganese(II) in the presence of isobutyraldehyde under an atmospheric pressure of molecular oxygen at room temperature. The kind of aldehyde and aldehyde/styrene molar ratio greatly influenced the reaction. The catalyst could be recycled, but after recycling for five times, the yield of styrene oxide decreased from 96.0% to 84.6%.     

晶粒尺寸对Pr0.5(Ca0.47Ba0.03)MnO3中台阶效应的影响

采用溶胶-凝胶法制备了不同颗粒尺寸的Pr0.5(Ca0.47Ba0.03)MnO3多晶样品.对样品进行电阻测量发现,随颗粒边界的减小,其电阻率随磁场的变化即ρ(H)曲线上台阶数目和位置发生变化;实验同时发现,热循环对样品低温下的基态也有很大的影响.实验结果表明,颗粒尺寸大小,可以有效地调节反铁磁相(AFM)和铁磁相(FM)之间的相互作用,从而对台阶效应产生影响.进一步证明了台阶效应与相应力有关.     

高温超导线(带)材的研究进展

综述了高温超导线(带)材的最新研究进展。主要介绍了第一代铋系高温超导线材,第二代钇系高温超导涂层带材以及新型MgB2超导线材的研究现状,并探讨了其发展方向和研究重点。     

The synthesis and characterization of C60 chemically modified poly(N-vinylcarbazole)

Addition of C₆₀ moiety, a powerful electron acceptor to poly(N-vinylcarbazole) (PVK) by chemical reaction modifies considerably the physical and chemical properties of PVK. The characterization techniques employed are UV-visible, IR, DSC, TGA, ESR, ¹³C-NMR spectroscopy, scanning electron microscopy, XRD, and cyclic voltammetry. The fullerenated PVK, which has a visibly earthy yellow cast when compared with the unreacted polymer, has a new structure in the UV-vis absorption spectrum with the active range extending from about 280 to 870 nm, its apparent temperature sensitivity is intriguing, and an unusual temperature dependence for the ESR spectrum is observed. Considerable difference of electronic structure between pure PVK and C₆₀-PVK copolymer is indicated. The thermal stability and oxidation-reduction activation of pure PVK are enhanced by C₆₀-chemical modification. © 1996 John Wiley & Sons, Inc.