用Co(naph)2-Al2(C2H5)3Cl3-P(OPh)3催化体系合成中乙烯基液体聚丁二烯

为获得适中乙烯基含量的液体聚丁二烯为目的, 对Co(naph)2-Al2(C2H5)3Cl3-P(OPh)3催化体系进行了较为系统的研究, 考察了该体系的催化剂配比、浓度及供电子试剂对分子量、微观结构和转化率的影响. 实验结果表明, 该体系在一定的条件下可以制备出分子量在700~3500、1,2结构含量在35%~40%且转化率高于55%的液体聚丁二烯.     

用复合调节剂合成异戊二烯-苯乙烯共聚物的反应动力学

以正丁基锂为引发剂,环己烷为溶剂,十二烷基苯磺酸钠/四氢呋喃(SDBS/THF)为复合调节剂,采用负离子溶液聚合法制备了异戊二烯-苯乙烯共聚物,考察了反应温度,复合调节剂用量对聚合反应的影响,研究了聚合反应动力学,求取了聚合反应的表观反应速率常数kp",通过Arrehenius方程求得了不同反应条件下的聚合反应活化能,并对聚合物的微观结构进行了研究,结果表明,十二烷基苯磺酸钠/四氢呋喃(SDBS/THF)复合调节剂对合成异戊二烯-苯乙烯共聚物是有效的微观结构调节剂。     

磷钨酸铜绿色催化合成缩醛(酮)及其催化活性测定

合成了绿色杂多酸盐催化剂磷钨酸铜;将环己酮、苯甲醛同乙二醇、1,2-丙二醇的缩合反应作为探针反应,测定了催化剂的催化活性,比较系统地考察了催化剂用量、物料配比、反应时间、带水剂用量等因素对反应产率的影响.结果表明:在底物醛(酮)用量0.2 mol、醛(酮)/乙二醇(1,2-丙二醇)摩尔比1.0/1.5、催化剂用量0.5 g、带水剂环己烷用量18 mL、一定温度下回流反应2.0 h,1,4-二氧螺[4,5]癸烷产率为83.3%,3-甲基-1,4-二氧螺[4,5]癸烷产率为89.7%,2-苯基-1,3-二氧环戊烷产率为66.7%,4-甲基-2-苯基-1,3-二氧环戊烷产率为78.5%.     

环戊烷和环己烷在silicalite-1分子筛上的热脱附行为

采用智能质量分析仪(IGA)及TG/DTG法研究了环戊烷和环己烷在硅沸石silicalite-1上的热脱附行为。当环戊烷在silicalite-1上吸附量小于4 m/uc时,TG/DTG曲线表明环戊烷在silicalite-1上存在一个脱附过程。吸附量大于4 m/uc,TG曲线显示热脱附过程明显分为两个阶段,DTG曲线中出现两个明显的脱附峰,彼此分离。环己烷在silicalite-1上只存在一种脱附过程,DTG曲线只出现一个脱附峰。从环戊烷和环己烷的热脱附曲线中也可看出,随着吸附量的增加脱附峰温逐渐向高温方向偏移。     

三元共聚物聚甲基乙撑-环己撑碳酸酯的合成与表征

报道了三元共聚物聚甲基乙撑-环己撑碳酸酯的制备与性能研究. 实验采用高活性的负载戊二酸锌作为催化剂, 在不添加任何溶剂的情况下, 以二氧化碳和环氧丙烷、环氧环己烷为原料, 制备了不同环己撑碳酸酯含量的三元共聚物, 并对其结构和热性能、力学性能进行了表征和分析. 结果表明这些三元共聚物具有较高的分子量, 且玻璃化转变温度随着主链上的环己撑碳酸酯含量增加而逐渐升高. 同时三元共聚物表现出比二元共聚物更好的力学性能.     

负离子合成POSS端基官能化聚苯乙烯

以苯乙烯为单体、氯丙基七异丁基多面体低聚倍半硅氧烷(chloropropyllsobutyl POSS,POSS-Cl)为封端剂、正丁基锂(n-Bu Li)为引发剂、环己烷为溶剂、四氢呋喃(THF)为结构调节剂,采用阴离子聚合技术,合成了POSS端基官能化聚苯乙烯(PS-POSS).采用核磁共振仪(1~H-NMR、~(13)C-NMR)和凝胶渗透色谱仪(GPC)对PS-POSS的结构和分子量分布进行了表征,证明了POSS与聚苯环乙烯锂(PSLi)发生了封端反应生成PSPOSS;封端后分子量分布略有加宽,特别是相比传统有机封端剂,没有二聚等副产物生成.考察了引发剂种类、结构调节剂用量、POSS用量、PS分子量、封端反应温度和时间等因素对PS-POSS封端效率的影响.结果表明,在THF/n-BuLi摩尔比大于5、POSS/n-BuLi摩尔比等于1.1、反应温度为60℃、反应时间为30 min时,封端效率最高,达到80%以上;而随着PS数均分子量增加,封端效率逐渐降低.     

ZnZSM-5沸石上某些环烷烃芳构化性能的研究

用脉冲微反技术研究了环己烷、甲基环己烷和甲基环戊烷在ZnZSM-5和HZSM-5上反应的产物分布和动力学、发现在ZnZSM-5上, 环己烷和甲基环戊烷以高选择性转化成苯, 甲基环己烷以高选择性转变为甲苯; 在HZSM-5上它们反应的芳烃选择性均很低且都得到以甲苯为主的BTX混合物。证明了这些反应都为动力学一级反应,求出了370 ℃—450 ℃间反应的速度常数和活化能。还发现环己烷反应的苯选择性与催化剂中的Zn含量有一致的对应关系。提出了ZnZSM-5上环烷烃反应的过程图式, 认为芳构化过程的控制步骤是环状碳离子的形成, 反应中非预计芳烃组分的产生与中间体环状碳离子的低温烷基化和高温脱烷基以及裂解所产生的小分子的再芳构化有关。     

负载钛系催化剂催化合成高反式丁二烯-异戊二烯共聚物

采用负载钛系催化剂 [TiCl4 MgCl2 (i Bu) 3Al]催化丁二烯 (Bd) 异戊二烯 (Ip)共聚合 ,研究了单体配比、聚合温度、烷基铝浓度和催化剂浓度及单体浓度等对共聚合速率及共聚物特性粘数的影响 .结果表明 ,当单体配比中Bd (Bd +Ip)摩尔百分比≤ 2 0 % ,可制得高分子量的共聚物 .IR光谱分析及1 H NMR分析表明所得共聚物为高反式 1,4 结构 ,丁二烯单体单元的反式 1,4 含量大于 90 % ,异戊二烯单体单元的反式 1,4 含量大于 98% ,共聚物中丁二烯含量高于单体初始配比中的含量 .在一定的载钛量下 ,聚合条件对共聚物的微观结构影响不大     

用可溶性催化剂合成顺式聚丁二烯的研究——Ⅰ.用CoCl2·4C5H5N-(C2H5)2AlCl作催化剂

本文研究了催化剂的用量、单体的浓度、聚合温度等聚合条件对聚丁二烯的转化率、分子量以及链结构的影响。试验结果表明:这个催化剂的特点是催化剂用量极少,1,4-顺式含量高而且稳定,聚合速度太快,高聚物的分子量过大,因此进一步研究了聚合速度的控制和高聚物分子量的调节。已得到的结果是:(1)在不同溶剂中聚合的速度相差甚大。其快慢的顺序是,苯>甲苯>二甲苯>三甲苯。(2)添加一些如苯基-β-萘胺、N,N′-二苯基对苯二胺等胺类,既可减慢聚合速度,又能降低高聚物的分子量。(3)调节体系中水分的含量,控制高聚物的分子量。(4)利用二种溶剂混合的不同比例,调节高聚物的分子量。(5)加入少量的萘、蒽等稠环芳烃于庚烷溶剂中,则大大提高高聚物的分子量。对上述结果进行了讨论。     

天然气水合物分解热的确定

利用可视化高压流体测试系统研究了6个体系（甲烷、合成天然气、甲烷－环己烷、甲烷－环戊烷、甲烷－甲基环己烷（MCH）、合成天然气－甲基环己烷）水合物的形成条件，根据水合物相平衡数据应用Clausius-Clapeyron方程计算了Ⅰ型、Ⅱ型和H型水合物的分解热，结果表明水合物分解热与填充水合物晶格的气体分子直径有关。     

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。     

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.     

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.

     

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。