自组装和共缩聚法制备磺酸基修饰的硅柱磷酸锆

以十六胺插层磷酸锆为原料,利用十二烷基二甲基苄基氯化铵为导向模板剂,通过正硅酸乙酯和巯丙基三甲氧基硅烷的层间共水解缩聚,并结合双氧水对巯丙基的熏蒸氧化,制备了磺酸基修饰的硅柱磷酸锆材料。通过XRD、SEM、N2吸附-脱附和FT-IR等方法对柱撑材料进行了结构表征。结果表明,通过调变预撑剂和模板剂中的碳链长度可以优化材料的柱撑结构和孔结构,磺酸基修饰的材料孔径分布在2.17 nm左右,比表面积可达163 m2·g-1,且保留有规整有序的柱撑磷酸锆层板结构。磺酸基的修饰则成功调变了材料的酸位性质,Br觟nsted酸量最高可达2.71 mmol·g-1,总酸量可达5.20 mmol·g-1。利用柠檬酸与正丁醇的酯化反应为探针反应,由于磺酸基修饰的硅柱磷酸锆材料具有独特的空间反应效应和较为丰富的Br觟nsted酸位,酯化反应转化率最高可达95.74%。     

氧化硅柱撑磺化磷酸-苯膦酸锆的合成及性能

以磷酸-苯膦酸锆为层板,合成并表征了硅柱撑的层柱磷酸-苯膦酸锆,并磺化了其中的苯环.磺化后的产物具有较高的酸量,在酯化反应中催化活性与硫酸相当.     

自组装和共缩聚法制备磺酸基修饰的硅柱磷酸锆

以十六胺插层磷酸锆为原料, 利用十二烷基二甲基苄基氯化铵为导向模板剂, 通过正硅酸乙酯和巯丙基三甲氧基硅烷的层间共水解缩聚, 并结合双氧水对巯丙基的熏蒸氧化, 制备了磺酸基修饰的硅柱磷酸锆材料。通过XRD、SEM、N2吸附-脱附和FT-IR等方法对柱撑材料进行了结构表征。结果表明, 通过调变预撑剂和模板剂中的碳链长度可以优化材料的柱撑结构和孔结构, 磺酸基修饰的材料孔径分布在2.17 nm左右, 比表面积可达163 m²·g^-1, 且保留有规整有序的柱撑磷酸锆层板结构。磺酸基的修饰则成功调变了材料的酸位性质, Brönsted酸量最高可达2.71 mmol·g^-1, 总酸量可达5.20 mmol·g^-1。利用柠檬酸与正丁醇的酯化反应为探针反应, 由于磺酸基修饰的硅柱磷酸锆材料具有独特的空间反应效应和较为丰富的Brönsted酸位, 酯化反应转化率最高可达95.74%。     

氧化锆层柱磷酸锆的制备及性能

考察了不同制备因素对形成氧化锆层柱磷酸锆的影响,发现适中的锆离子浓度,较低的反应温度及较长的反应时间有利于形成稳定的氧化锆层柱磷酸锆。样品经250℃焙烧后形成较为规整的层柱结构,氧化锆柱与层板间以P-O-Zr键相连,比表面为107～183m^2/g,孔径较集中地为2.5nm。层柱样品表面只存在L酸位,无B酸位。对异丙醇脱水反应和苯甲醛还原反应有较好的反应活性,其比活性优于纯的氧化锆,表明它具有良好的酸催化和酸碱双功能催化作用。     

磺化苯膦酸-磷酸锆的制备及其对甲醛羰基化反应的催化性能

合成了苯膦酸锆及其混合配体形式的苯膦酸.磷酸锆和苯膦酸-亚磷酸锆,并通过层间苯环磺化制备了不同组成的磺化苯膦酸-磷酸锆(SZrPP-n).利用电感耦合等离子体、X射线衍射、热重、红外光谱等手段对样品磺化前后的结构和性质进行了表征,考察了SZrPP-n对甲醛羰基化反应的催化性能.结果表明.苯膦酸.磷酸锆具有典型的层状结构,改变合成条件可以得到层间距不同的晶体.磺化后,SZrPP-n样品层间距增大,具有丰富的酸性位,热稳定性可以达到200℃以上.SZrPP-n对甲醛羰基化制乙醇酸甲酯反应具有较高的催化活性和稳定性.     

氧化锆层柱鳞酸锆的制备及性能

考察了不同制备因素对形成氧化锆层柱磷酸锆的影响,发现适中的锆离子浓度,较低的反应温度及较长的反应时间有利于形成稳定的氧化锆层柱磷酸锆.样品经250℃焙烧后形成较为规整的层柱结构,氧化锆柱与层板间以P-0-Zr键相连,比表面为107～183m2/g,孔径较集中地为2.5nm.层柱样品表面只存在L酸位,无B酸位.对异丙醇脱水反应和苯甲醛还原反应有较好的反应活性,其比活性优于纯的氧化锆,表明它具有良好的酸催化和酸碱双功能催化作用.     

多孔层柱磷酸锆在Prins缩合反应中的应用

制备了一系列不同离子交换的多孔氧化硅层柱磷酸锆, 利用N₂吸附-脱附、 扫描电子显微镜和吡啶吸附红外光谱等方法对材料的结构和酸性进行了表征, 并应用于β-蒎烯与多聚甲醛的Prins缩合反应合成诺卜醇. 结果发现, 层柱磷酸锆对此反应具有优异的催化性能, 锌离子的引入可进一步提高诺卜醇的选择性, 从而得到更高的诺卜醇产率, 于80℃反应4 h后β-蒎烯的转化率为91%, 诺卜醇产率达到83%. 酸性表征结果表明, 诺卜醇产率与催化剂表面Lewis酸(L酸)性位的数目以及L酸位/B酸位的比值密切相关. 该催化剂还具有较好的重复利用性能, 反应5次后产率仅下降12%. 催化剂的失活可能是由于酸性位被积碳覆盖所致.     

合成皂石及其交联物在偏三甲苯歧化反应中的催化行为

以羟基铝低聚物与其交联制得柱撑皂石,并在偏三甲苯歧化反应中考察了它们的催化性能.结果表明,催化活性随柱撑皂石表面酸量增加而增加;四甲苯中均四甲苯和二甲苯中邻二甲苯的百分含量皆高于热力学平衡值.催化特性与柱撑皂石的柱密度相关.     

羟基铝柱撑二硫化钼的制备及其催化加氢性能

 采用单分子层技术将羟基铝聚合物Al7+13阳离子嵌入到二硫化钼板层间,得到层间距为1.488～1.599 nm的柱撑复合材料. X射线粉末衍射等研究表明,羟基铝聚合物Al7+13经60 ℃恒温陈化2 d即可作为稳定的柱撑液使用; 在柱撑反应体系中,较小的Al/Mo摩尔比有利于获得客体物种较均一和结晶度较好的柱撑复合材料. 与原料 2H-MoS2 相比,柱撑二硫化钼的层间距增大,晶粒变小,比表面积增加. 差示扫描量热分析结果表明,柱撑材料具有较好的热稳定性. 选择苯饱和加氢反应为探针,测定了柱撑材料的催化活性. 气相色谱测定结果表明,柱撑二硫化钼的催化性能显著优于未柱撑的 2H-MoS2 和Raney Ni催化剂. 这与柱撑材料比表面积的增大、可能存在的缺陷增多而导致活性位增多以及对氢气的有效吸附增加有关.     

氧化铬层柱磷酸锆的制备及催化性能

详细研究了有机胺品种、层板预撑态、水解度以及Ｃｒ加入量等制备因对氧化铬层柱磷酸铬结构和性能的影响，用乙胺胶体化法制备的氧化铬层柱磷酸锆比表面积可高达４８２ｍ＾２／ｇ，而孔径集中在２．６ｎｍ附近，层板胶体化时表面磷酸根的知度水有利于提高支柱产品的比表面和形成规整的平板型层间孔，用ＴＧ，ＩＲ，ＸＲＤ和Ｎ２吸附等温线方法研究了氧化铬柱了的形成过程和热稳定性，异丙醇脱水和异丙苯裂解反应结果表明，氧化铬层柱     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。