氧化法玉米淀粉胶的制备和改性及其在内墙涂料中的应用

面临石油危机和环境恶化的双重威胁,作为石油替代品,天然高分子的开发利用又一次成为高分子材料研究领域的热点之一。本文以双氧水为氧化剂,硫酸亚铁为催化剂,将玉米淀粉氧化变性后,和苯乙烯及丙烯酸酯单体接枝共聚,获得改性玉米淀粉胶,并以其作为基料,复配得到改性玉米淀粉胶内墙涂料,明显改善了涂料的贮存稳定性和涂膜的附着力、流平性、耐水性、抗飞溅性等性能,是一种环境友好、成本低廉的内墙涂料。     

Palladium‐Catalyzed Three‐Component Reaction of 3‐(Tri‐n‐ butylstannyl)allyl Acetates,Aldehydes, and Triorganoboranes: An Alternative to the Carbonyl Allylation Using α,γ‐Substituted Allylic Tin Reagents

A three‐component reaction of 3‐(tri‐n‐butylstannyl)allyl acetates, aldehydes, and triorganoboranes in the presence of a palladium‐Xantphos catalyst system predominately gave (E)‐anti‐homoallylic alcohols with high diastereoselectivity and good to high levels of alkene stereocontrol. An efficient chirality transfer was observed when an enantioenriched substrate was employed. The reaction was initiated by the formation of an allylic gem‐palladium/stannyl intermediate, which subsequently underwent allylation of the aldehyde by an allyltributyltin followed by a coupling reaction of the in‐situ‐generated (E)‐vinylpalladium acetate with the triorganoborane.

     

Planar‐Chiral Cyclopentadienyl‐Ruthenium‐Catalyzed Regio‐ and Enantioselective Asymmetric Allylic Alkylation of Silyl Enolates under Unusually Mild Conditions

We report the asymmetric allylic alkylation of allylic chlorides with silyl enolates as a carbon nucleophile using a planar‐chiral cyclopentadienyl‐ruthenium (Cp′Ru) catalyst. The reaction proceeds under unusually mild conditions to give the desired branched products with complete regioselectivity and high enantioselectivity, and reactive functional groups, such as aldehyde, can be tolerated. In this reaction system, Cp′Ru plays an important role in activating both silyl enolate and allylic chloride.

     

Fabrication and characterization of Si3N4 whisker-reinforced SiO2 ceramic for radome materials

Fused silica ceramic has become one of the most widely used radome materials in the world since the 1970s. But its poor mechanical properties restricted its application to some extent. To improve the mechanical properties of the fused silica ceramic and keep its characteristic for radome materials, silicon nitride (Si₃N₄) whisker-reinforced fused silica ceramics were prepared by a slip-casting method in the work. The influence of Si₃N₄ whisker contents on the properties of the slurry was studied, indicating that the preferable pH values of the slurry were 4–6 and whisker contents were 10 wt.%. The flexural strength of as-prepared Si₃N_4w/SiO₂ ceramic was about 74.35 MPa, exhibiting an increase of 7.75% over that of the pure silica sample. Its dielectric constant in the range from 8 to 12 GHz and tanδ under 10 GHz were, respectively, 3.37 and .0011. It is of great interest to find that Si₃N_4w/SiO₂ has excellent oxidization resistance and its mass maintains even at 1270°C.     

膨胀石墨的化学氧化法制备的研究进展

本文通过从石墨原料、氧化剂、膨化温度和膨胀设备等4个方面进行分析,综述了膨胀石墨的化学氧化法制备的研究进展,并提出了膨胀石墨的研究方向:采用细鳞片石墨,在少用甚至不用硫酸、膨化温度较低的情况下,制备高倍率低硫甚至无硫低温膨胀石墨。     

HClO4氧化对石油焦基活性炭超级电容器性能的影响

采用HClO4对石油焦进行氧化改性,按照碱碳比为3∶1的比例将改性石油焦活化成活性炭,产物标记为OAC-3.作为对比,按照碱碳比4∶1将石油焦活化成活性炭,产物标记为AC-4.采用XRD、I2吸附、N2吸附和循环伏安研究HClO4氧化对石油焦结构和产物活性炭性能的影响.结果表明,HClO4氧化将石油焦石墨微晶d(002)晶面层间距由0.344nm提高到0.353nm,同时将晶粒粒径由2.34nm减小到1.75nm.AC-4和OAC-3的比表面积分别为2 929和3 058m2/g,在0.5 mV/s的扫描速率下,其比电容分别为361.3和392.7 F/g;基于OAC-3的超级电容器具有更好的功率特性.     

A direct synthetic route to allyl sulfides from cyclic Morita–Baylis–Hillman alcohols

p-TsOH-mediated the direct α-substitution of cyclic Morita–Baylis–Hillman alcohols with aliphatic and aromatic thiols in refluxing THF. The reaction proceeded with complete α-regioselectivity and provided the corresponding allyl sulfides in moderate to good yields.     

Comparative studies of normally-off Al0.26Ga0.74N/AlN/GaN/Si high electron mobility transistors with different gate structures

Systematic designs to achieve normally-off operation and improved device performance for Al_0.26Ga_0.74N/AlN/GaN high electron mobility transistors (HEMTs) grown on a Si substrate are investigated in this work. The step-by-step approach includes: (1) devising a thin AlGaN/AlN composite barrier, (2) introducing fluoride ions within the active region by using CF₄ plasma treatment, (3) growing the Al₂O₃ oxide passivation layers within gate-drain/source regions by using a cost-effective ozone water oxidization technique, and (4) integrating a metal-oxide-semiconductor gate (MOS-gate) design with high-k Al₂O₃ gate dielectric. Devices with four different evolutionary gate structures have been compared and studied. Variations of threshold voltage (V_th), Hooge coefficients (α_H), maximum drain-source current density (I_{DS, max}), maximum extrinsic transconductance (g_{m, max}), gate-voltage swing (GVS) linearity, two-terminal gate-drain breakdown/turn-on voltages (BV_GD/V_on), on/off current ratio (I_on/I_off), and high-temperature characteristics up to 450 K are also investigated.     

铼(Ⅶ)催化烯丙醇移位/去对称化串联反应

使用Re_2O_7和手性磷酸为共催化剂,实现了催化不对称的环己二烯酮烯丙醇移位/氧杂-Michael加成串联反应。通过这一反应,可以一步构建带有三个手性中心的环己烯酮骨架结构,为合成带有这一类骨架的天然产物和药物分子提供了高效的合成方法。同时,通过分析条件的优化,找到了合适的手性拆分条件,为光学活性环己烯酮化合物提供了分析方法。     

钛精矿流态化预氧化氢还原试验研究

钛精矿流态化氢气还原生产高钛渣技术不仅原料选择范围广、能耗低,而且可实现清洁生产。在冷态试验基础上对钛精矿在高温下先氧化再还原试验进行了探索,研究了温度、还原时间、p(N2)/p(H2)和粒度对金属Fe还原率的影响。试验结果表明:800～950℃,随着还原温度的升高,Fe的金属化率有较明显的增加;在同一温度下,Fe的金属化率随时间延长先快速增加而后趋缓;随着粒径的减小,钛精矿的Fe还原率提高较明显;氢气的浓度对钛精矿还原影响至关重要,随着氢气浓度的增加,还原率有着明显的提高。