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991.
992.
Werner Uhl Prof. Dr. Henrik Rene Bock Dipl.‐Chem. Michael Claesener Dr. Marcus Layh Dr. Ines Tiesmeyer Dipl.‐Chem. Ernst‐Ulrich Würthwein Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(36):11557-11564
Treatment of (silylalkynyl)benzenes with (Me3C)2Ga? H afforded stable cis‐addition products, for example, (Me3C)2Ga? C(SiMe3)?C(H)? C6H5 ( 1 ), while spontaneous cis/trans rearrangement was observed for sterically less shielded gallium hydrides. The corresponding trans‐di(tert‐butyl)gallium compounds ( 13 , 14 ) were obtained by the reaction of C6H6?n[C(H)?C(SiMe3)GaCl2]n ( 11 , 12 ) with LiCMe3. In contrast, spontaneous isomerization took place upon reaction of (Me3C)2Al? H with phenyltrimethylsilylethyne. In this case the cis isomer ( 17 ) was detected only at low temperature, while the trans product ( 18 ) formed quantitatively above 0 °C. Quantum‐chemical calculations showed that the trans forms are thermodynamically favored, essentially caused by a better mesomeric interaction of the C?C double bonds with the phenyl groups, a smaller steric stress in the molecules, and a short bonding contact of the coordinatively unsaturated Al or Ga atoms to C? H bonds of the aromatic rings. The rotation about the C?C double bonds follows a zwitterionic mechanism, and the relatively small rotational barrier is further lowered by an interaction to a Lewis acidic lithium cation. 相似文献
993.
Pang X Du H Chen X Wang X Jing X 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(10):3126-3136
A series of enolic Schiff base aluminum(III) complexes LAlR (where L=NNOO-tetradentate enolic Schiff base ligand) containing ligands that differ in their steric and electronic properties were synthesized. Their single crystals showed that these complexes are five-coordinated around the aluminum center. Their coordination geometries are between square pyramidal and trigonal bipyramidal. Their catalytic properties in the solution polymerization of racemic lactide (rac-LA) were examined. The modifications in the auxiliary ligand exhibited a dramatic influence on the catalytic performance. Lengthening the backbone from C(2) alkylene to C(3) alkylene resulted in remarkable enhancement of both the stereoselectivity and the polymerization rate because of the increasing flexibility of the diimine backbone. Electron-withdrawing substituents in the diketone also highly improved the activity and the stereoselectivity. Among these complexes, 4 b had the highest activity and the stereoselectivity owing to the C(3) alkylene backbone and the two gem-methyl groups on the middle carbon atom. The value of the polymerization rate constant (k(p)) catalyzed by 4 b in 70 degrees C was 1.90 L mol(-1) min(-1), the activation energy of the polymerization (35.4 kJ mol(-1)) was calculated according to the Arrhenius equation. Other factors that influenced the polymerization, such as the polymerization time, the temperature, and the monomer concentration, are also discussed in detail. 相似文献
994.
铝阳极氧化膜的半导体特性 总被引:1,自引:0,他引:1
The semiconductor properties of anodic oxide film formed on commercial pure aluminum were analyzed usingMott-Schottky theory and point defect model (PDM). The donor density, oxygen vacancy diffusion coefficient and flat-band potential were measured for the oxide films sealed by boiling water and K2Cr2O7, respectively. The results indicated that the anodic oxide films showed the n-type semiconductor property and the donor density decreased exponentially with the voltage elevating. The value of oxygen vacancy diffusion coefficient is about (1.12-5.53)伊10-14 cm-2·s-1. The flat-band potential of anodic oxide filmdeclined after sealing. 相似文献
995.
强烈阳极氧化法快速制备多孔氧化铝模板 总被引:2,自引:0,他引:2
In the electrolyte of oxalic acid/alcohol/aqueous solution, highly-ordered porous anodic aluminum oxide(AAO) template was fabricated by hard anodization. The surface morphology and the structure of AAO template were characterized by Field-Emission Scanning Electron Microscope(FE-SEM) and XRD, respectively. The effects of different factors including alcohol type, ratio of alcohol to water, and oxalic acid concentration on the ordering degree and pore diameter of AAO template were investigated. Under the glycol to water ratio of 1∶1(by volume) with an oxalic acid concentration of 0.5 mol·L-1, and voltage at 160 V, the obtained AAO template was hexangular arrangement with pore diameter of 80 nm and pores spacing of 120 nm, the growth rate was 51.9 μm·h-1. 相似文献
996.
Preparation and characterization of a novel strong-fluorescent hydrotalcite-like compound (Al-HTLc) 总被引:3,自引:0,他引:3
A novel strong-fluorescent hydrotalcite-like compound (Al-HTLc) was synthesized by coprecipitation. In the sample, the content of aluminum(III) in the layers was decreased to a proper value. The Al3 ions coordinated with 8-hydroxyquinolines (8-HQ) which were dispersed into the anions in the interlayer region. The sample was characterized by XRD, XPS, FT-IR, TG-DSC, UV-Vis, and fluorescence spec- troscopy; its composition and structure were also determined. The results indicate that the sample can emit fluorescence (487 nm) with a strong fluorescence intensity (4.9×105 (a.u.)). The fluorescent lifetime and fluorescence quantum yield of Al-HTLc were measured to be 21.24 ns and 67%, respectively, higher than those of pure 8-hydroxyquinoline aluminum (Alq3). The result of TG-DSC measurement clearly shows the enhanced thermal stability of Al-HTLc compared with that of MgAl-LDH and pure Alq3. Al-HTLc may be used as a novel luminescent functional material. 相似文献
997.
998.
A series of benzoylacetone-imine ligands, PhCOCHCMeNHR ( L 1 H , R = CH2Ph; L 2 H , R = CH2Ph-4-Me; and L 3 H , R = CH2Ph-4-OMe), are first synthesized following the condensation of benzoylacetone and 4-substituted benzylamine. Later, reacting L 1 H – L 3 H with one equivalent of AlMe3 in toluene, the monomeric Al derivatives are generated, (PhCOCHCMeNR)AlMe2 ( 1 , R = CH2Ph; 2 , R = CH2Ph-4-Me; 3 , R = CH2Ph-4-OMe). All the ligands and metal derivatives are characterized by 1H and 13C NMR spectroscopy. Single crystal X-ray diffraction analysis reveals the geometry of all ligands and complex 2 . As supporting catalysts, the Al derivatives, 1 – 3 , are effective to initiate the coupling of CO2 and styrene oxide to form cyclic carbonates. Although employing TBAI (tetra-n-butylammonium iodide), TBAC, tetrabutylammonium chloride, and TBAB (tetra butyl ammonium bromide) as cocatalyst, the optimized catalytic system exhibits the best conversion of epoxide in presence of TBAI under the reaction temperature and time, respectively, 90°C and 6 hr, respectively. The ring opening polymerization of ε-caprolactone is also appraised subjecting the Al derivatives, 1 – 3 , as catalysts in presence of benzyl alcohol and all the conversions of ε-caprolactone reach over 95% at the reaction condition of 100°C and 1 hr. 相似文献
999.
Xiaoyu Xu Zhuyu Bai Xincheng Guo Yao Chen Xiaolang Chen Zongcheng Lu Hong Wu 《先进技术聚合物》2023,34(1):195-204
Driven by global environmental issues, the development of green building materials has become an immediate focus. In this work, n-pentane was used as an environmentally friendly blowing agent to prepare flame-retardant rigid polyurethane foam (RPUF) with the addition of expandable graphite (EG) successfully, and the effect of n-pentane content on flame retardancy and compressive properties of RPUF/EG composites was investigated through limit oxygen index (LOI), vertical burning test (UL-94), scanning electron microscope (SEM), thermogravimetric analysis (TGA), and compressive properties test. SEM results show that the content of EG and n-pentane causes a change in the cell structure of RPUF. The change of the n-pentane content has also an obvious effect on the thermal stability, flame retardancy, and specific compressive strength of RPUF/EG composites. In addition, the cell structure of RPUF matrix has an obvious influence on the distribution of EG in the composites, which indirectly affects the flame-retardant efficiency of EG. This research explores the conditions for the application of environmentally friendly RPUF and expands its application prospects. 相似文献
1000.
Zn(II) ions sorption onto N‐Benzoyl‐N‐Phenylhydroxylamine (BPHA) impregnated polyurethane foam (PUF) has been studied extensively using radiotracer and batch techniques. Maximum sorption (~98%) of Zn(II) ions (8.9 × 10?6 M) onto sorbent surface is achieved from a buffer of pH 8 solution in 30 minutes using 7.5 mg/mL of BPHA‐impregnated polyurethane foam at 283 K. The sorption data follow Langmuir, Freundlich and Dubinin‐Radushkevich (D‐R) isotherms. The Langmuir constants Q = 18.01 ± 0.38 μ mole g?1 and b = (5.39 ± 0.98) × 103 L mole?1 have been computed. Freundlich constants 1/n = 0.29 ± 0.01 and Cm = 111.22 ± 12.3 μ mole g?1 have been estimated. Sorption capacity 31.42 ± 1.62 μ mole g?1, β = ?0.00269 ± 0.00012 kJ2 mole?2 and energy 13.34 ± 0.03 kJ mole?1 have been evaluated using D‐R isotherm. The variation of sorption with temperature yields ΔH = ?77.7 ± 2.8 k J mole?1, ΔS = ?237.7 ± 9.3 J mole?1 K?1 and ΔG = ?661.8 ± 117.5 k J mol?1 at 298 K reflecting the exothermic and spontaneous nature of sorption. Cations like Fe(III), Ce(III), Al(III), Pb(II) and Hg(II) and anions, i.e., oxalate, EDTA and tartrate, reduce the sorption significantly, while iodide and thiocyanate enhanced the sorption of Zn(II) ions onto BPHA‐impregnated polyurethane foam. 相似文献