稀土复合固体酸SO_4~(2-)/TiO_2/La~(3+)催化合成马来酸二辛酯

研究了固体超强酸SO2 - 4/TiO2 /La3+用于合成马来酸二辛酯。并与硫酸对甲苯磺酸的催化效果比较。考察了Ti/La物质量比、硫酸浓度、焙烧温度对催化剂活性和反应时间对酯化反应的影响。结果表明 :当Ti/La物质量比为 6∶1、浸渍液硫酸浓度为 1 8mol/L、在5 5 0℃下焙烧时具有最高的催化活性 ,用于马来酸酐和正辛醇的酯化反应可得无色透明的酯化产物 ,3h内酯化率达 96 9%。     

稀土复合固体酸SO4^2—／TiO2／La^3＋催化合成马来酸二辛酯

研究了固体超强酸SO4^2-/TiO2/La^3 用于合成马来酸二辛酯，并对硫酸对甲苯磺酸的催化效果比较，考察了Ti/La物质量比，硫酸浓度，焙烧温度对催化剂活性和反应时间对酯化反应的影响，结果表明：当Ti/La物质量比为6：1，浸渍液硫酸浓度为1．8mol/L，在550℃下焙烧时具有最高的催化活性，用于马来酸酐和正辛醇的酯化反应可得无色透明的酯化产物，3h内酯化率达96．9％。     

固体超强酸SO4^2—／TiO2催化合成马来酸二辛酯的研究

制备了固体超强酸SO42-/TiO2用于合成马来酸二辛酯。考察了硫酸浓度、浸渍时间、焙烧温度、焙烧时间对催化剂活性和反应时间对酯化反应的影响。结果表明:对于给定反应,当浸渍液硫酸浓度为0.5tool/L、浸渍时间为18h、在550℃下焙烧2h时催化剂具有最高的催化活性,用于马来酸酐和正辛醇的酯化反应可得无色透明的酯化产物,3h内酯化率达97.8％。     

固体超强酸SO24-/TiO2催化合成亚油酸乙酯

用两相滴定沉淀法制备了SO24-/TiO2固体超强酸催化剂,得到了适合亚油酸酯化的催化剂制备工艺条件:硫酸浸渍浓度0.75 mol/L,浸渍时间4 h,焙烧温度450℃,焙烧时间4 h.首次将该催化剂用于亚油酸的酯化反应催化合成亚油酸乙酯,考察了物料比、反应时间、催化剂用量对亚油酸与乙醇酯化反应的影响规律,最佳反应条件为:n(无水乙醇)/n(亚油酸)=4,w(催化剂)=3%(相对于亚油酸),反应时间8 h,亚油酸转化率可达93%.     

SO42-/WO3-ZrO2催化合成乙酸丁酯

制备了硫酸促进型酯化催化剂SO42-/WO3-ZrO2,考察了WO3含量、焙烧温度和焙烧时间等对酯化率的影响。结果表明催化剂适宜制备条件为：WO3含量10%,300℃焙烧2h;将其用于催化乙酸与正丁醇的酯化反应合成了乙酸丁酯,反应条件为：乙酸0.2mol,催化剂0.75g,n（正丁醇）∶n（乙酸）=1.8∶1,反应时间30min,酯化率可达98.2%。     

SO2-4/La2O3-ZrO2催化合成亚油酸乙酯

将SO2-4/ZrO2负载镧制备了新型催化剂SO2-4/La2O3-ZrO2,以亚油酸和乙醇的酯化反应为探针,考察了不同制备条件对催化剂性能的影响,结果表明,La3+浸渍浓度为0.07 mol/L,经110℃烘干后于500℃焙烧3 h所得催化剂活性最好.采用正交实验法对影响酯化反应的因素进行考察,最佳实验条件为n(醇):n(酸)= 6:1,反应时间6 h,催化剂用量3%(亚油酸),酯化率可达93.7%.且该催化剂具有良好的重复使用和再生能力.     

固体超强酸SO/TiO2催化合成亚油酸乙酯

用两相滴定沉淀法制备了SO24-/TiO2固体超强酸催化剂,得到了适合亚油酸酯化的催化剂制备工艺条件硫酸浸渍浓度0.75mol/L,浸渍时间4h,焙烧温度450℃,焙烧时间4h.首次将该催化剂用于亚油酸的酯化反应催化合成亚油酸乙酯,考察了物料比、反应时间、催化剂用量对亚油酸与乙醇酯化反应的影响规律,最佳反应条件为n(无水乙醇)/n(亚油酸)=4,w(催化剂)=3%(相对于亚油酸),反应时间8h,亚油酸转化率可达93%.     

SO42-/Fe2O3-Al2O3-TiO2固体超强酸的制备及催化活性研究

采用共沉淀法制备SO42-/FeO3-Al2O3-TiO2固体超强酸.通过正交实验考察了3种金属最佳配比,陈化时间,硫酸浸渍浓度,浸渍时间,焙烧温度,焙烧时间等因素对酸强度的影响.研究表明,SO42-/Fe2O3-Al2O3-TiO2固体超强酸最佳制备条件是:n(Fe):n(AL):n(Ti)=1:2:2,陈化时间3h,浸渍H2SO4浓度1.0mol·L-1,浸渍用量15mL·g-1,浸渍时问20min,焙烧温度500℃,焙烧时间5h.此外,还利用红外光谱对催化剂进行了结构表征,利用酯化反应对其催化活性进行了初步研究.     

固体超强酸SO_4~(2-)/TiO_2-SiO_2催化合成马来酸二辛酯

用H2 SO4浸渍钛硅复合氧化物 ,制得固体超强酸SO2 -4/TiO2 -SiO2 ,考察了催化剂对马来酸酐与正辛醇的酯化反应的催化作用及其制备条件对催化剂活性的影响 ,并与硫酸、对甲苯磺酸的催化效果比较。结果表明 :对于给定反应 ,当n(Ti)∶n(Si)为 15∶1、用浓度 0 .6mol/L的硫酸浸渍 8h、在 5 5 0℃下焙烧 3h时制得的催化剂SO2 -4/TiO2 -SiO2 具有最高的催化活性 ;用以催化马来酸酐和正辛醇的酯化反应 ,可得无色透明的酯化产物 ,3h内酯化率达 99.1% ;较SO2 -4/TiO2 催化剂的酯化率提高了约 6 %     

SO^2-4／ZrO2-La2 O3固体超强酸催化合成邻苯二甲酸二丁酯

采用ZrOCl2·8H2O和La(NO3)3·9H2O共沉淀法制备固体超强酸SO2-4/ZrO2-La2O3催化剂.固体超强酸SO2-4/ZrO2-La2O3制备条件为nZr/nLa为6 ∶ 1,-15 ℃陈化24 h,120 ℃干燥12 h,浸渍液硫酸浓度为0.5 mol/L,浸渍4 h,120 ℃干燥1 h,600 ℃焙烧4 h.将此固体超强酸用于邻苯二甲酸酐和正丁醇合成邻苯二甲酸二丁酯的酯化反应,考察了正丁醇和邻苯二甲酸酐的物质的量比、催化剂用量、反应时间、反应温度对酯化反应的影响.结果表明,醇酐的物质的量比为3.5 ∶ 1,催化剂用量为所用邻苯二甲酸酐的2.7%,反应时间3 h,反应温度160 ℃条件下酯化收率达91.6%.     

Wet Milling of Fe/Al/Al2O3 and Fe2O3/Al/Al2O3 Powder Mixtures

Wet milling of Al₂O₃-aluminide alloy (3A) precursor powders in acetone has been investigated by milling Fe/Al/Al₂O₃ and Fe₂O₃/Al/Al₂O₃ powder mixtures. The influence of the milling process on the physical and chemical properties of the milled powders has been studied. Particle refinement and homogenization were found not to play a dominant role, whereas plastic deformation of the metal particles leads to the formation of dislocations and a highly disarranged polycrystalline structure. Although no chemical reactions among the powder components in Fe₂O₃/Al/Al₂O₃ powder mixtures were observed, the formation of a nanocrystalline, ordered intermetallic FeAl phase in Fe/Al/Al₂O₃ powder mixtures caused by mechanical alloying was detected. Chemical reactions of Fe and Al particle surfaces with the atmosphere and the milling media lead to the formation of highly porous hydroxides on the particle surfaces. Hence the specific surface area of the powders increases, while the powder density decreases during milling. The fraction of Fe oxidized during milling was determined to be 0.13. The fraction of Al oxidized during milling strongly depends on the metal content of the powder mixture. It ranges between 0.4 and 0.8.     

Preparation and properties of poly(Nε,Nε-dicarboxymethyl-l-lysine)

A new ampholytic homopolypeptide, $\text{poly}\text{(N}{}^{\mathrm{\epsilon }}\text{,N}{}^{\mathrm{\epsilon }}\text{-}\text{dicarboxy-methyl-}\text{l}\text{-lysine}\text{)}$, which has one tertiary amino and two carboxyl groups in the side chain has been derived from a hydrochloride salt of poly(L-lysine). The polymer in aqueous solution seems to be in the coil form with locally extended structure (LES) at neutral pH. In both the acidic and alkaline regions, the molar ellipticity of the polymer changes as a result of change in net charge on the side chain. The conformational changes may be from the coil with LES to other coiled forms. 5–7 M NaClO₄ and 80% aqueous methanol induce the α-helix in the polymer at neutral pH. Divalent cations, Cu²⁺ and Ca²⁺, do not induce any remarkably ordered structures such as α-helix or β-structure in the polymer in aqueous solution at any pH. Ultraviolet absorption studies show an absorption peak of the polymer-Cu²⁺ complex near 240 nm. Dependence of the peak intensity on pH at various q values ($\text{q =}\text{[}\text{Cu}{}^{\mathrm{2+}}\text{]}\text{[}\text{residue}\text{]}$) indicates the two steps of the complex formation. At q less than 0.64, the formation is described only with the first step. An average coordination number for Cu²⁺ at the first step was calculated to be about 2 by the method of Mandel and Leyte. The association constant of Cu²⁺ with the residue at the step was determined from the absorption data to be far smaller than that for the Cu²⁺-EDTA complex. The second step of the formation occurs in the case of large q but the absorption data for the second step cannot be obtained exactly due to precipitation.     

Sintering of Si3N4-Y2O3-Al2O3

Sintering kinetics of the system Si₃N4-Y2O₃-Al₂O3 were determined from measurements of the linear shrinkage of pressed disks sintered isothermally at 1500° to 1700°C. Amorphous and crystalline Si₃N₄ were studied with additions of 4 to 17 wt% Y₂O₃ and 4 wt% A1₂O₃. Sintering occurs by a liquid-phase mechanism in which the kinetics exhibit the three stages predicted by Kingery's model. However, the rates during the second stage of the process are higher for all compositions than predicted by the model. X-ray data show the presence of several transient phases which, with sufficient heating, disappear leaving mixtures of β ' -Si₃N₄ and glass or β '-Si₃N₄, α '-Si₃N₄, and glass. The compositions and amounts of the residual glassy phases are estimated.     

Ag2O-Doped Bi2Sr2Ca1Cu2Ox Superconductors Prepared via Melt-Quenching

Ag₂O-doped superconducting Bi₂Sr₂Ca₁Cu₂O _x ceramics were prepared by a melt-quenching–reheating method. It is found that the Ag₂O-doped, as-cast specimens exhibit superconductivity ( T _c= around 80 K) by heat treatment at temperatures around 800°C even in an evacuated and sealed silica glass tube, while the undoped specimens do not and vaporize by the corresponding heat treatment. Conversion of the Ag₂O-doped, as-cast specimens into superconducting ceramics when heated in an evacuated vessel is explained in terms of the oxygen donor of Ag₂O in the specimen. This finding enables us to fabricate a desired shape of superconducting Bi₂Sr₂Ca₁Cu₂O _x ceramics sealed in metals or glasses. The addition of Ag₂O to Bi₂Sr₂Ca₁Cu₂O _x melt, however, had deleterious influences on the superconducting properties ( T _c and J _c) of the resultant ceramics when obtained by heat treatment in air.     

Participation of lewis base on vinyl chloride polymerization with Al(C2H5)3CCl4 catalyst system

The polymerization of vinyl chloride has been investigated using an $\text{Al}\text{(}\text{C}{}_2\text{H}{}_5\text{)}{}_3\text{CCl}{}_4$ catalyst system in the presence of various Lewis bases. Effective Lewis bases are γ-butyrolactone, diglyme and diethylenetriamine which are multidentate. The rate of polymerization is dependent not only on the basicity of the Lewis base used but also on a coordination number of one. The latter is the predominant factor. For the effect of polymeric amines, a tentative hypothesis is discussed.     

The System Si3N4-SiO2-Y2O3

Subsolidus phase relations were established in the system Si₃N₄-SiO₂-Y₂O₃. Four ternary compounds were confirmed, with compositions of Y₄Si₂O₇N₂, Y₂Si₃O₃N₄, YSiO₂N, and Y₁₀(SiO₄)₆N₂. The eutectic in the triangle Si₃N₄-Y₂Si₂O₇-Y₁₀(SiO₄)₆N₂ melts at 1500°C and that in the triangle Si₂N₂O-SiO₂-Y₂Si₂O₇ at 1550°C. The eutectic temperature of the Si₃N₄-Y₂Si₂O₇ join was ∼ 1520°C.