二乙基二烯丙基氯化铵均聚及其与丙烯酰胺或丙烯酸共聚动力学研究

采用膨胀计法研究了以过硫酸铵为引发剂,二乙基二烯丙基氯化铵(DEDAAC)在水溶液中的均聚及其与丙烯酰胺(AM)和丙烯酸(AA)共聚动力学,测定了相应的聚合表观活化能;采用元素分析法测定了DEDAAC分别与AM和AA在低转化率下共聚物的组成,并采用氯离子选择性电极法测定了DEDAAC-AM共聚物中的氯离子含量,按Kelen-Tudos方法求得了相应的竞聚率.结果表明,DEDAAC均聚速率方程为RP=k[M]0.99[I]0.76,表观活化能Ea=77.00kJ/mol,说明链终止为单基终止和双基终止并存,引发过程与单体浓度无关;DEDAAC与AM在摩尔比为4∶1时,共聚动力学方程为RP=[M]2.53[I]0.90,表观活化能Ea=67.06kJ/mol,单体竞聚率为rDE=0.31±0.02、rAM=5.27±0.53;DEDAAC与AA在摩尔比为4∶1时,共聚动力学方程为RP=k[M]2.94[I]0.83,表观活化能Ea=70.07kJ/mol,竞聚率为rDE=0.28±0.03、rAA=5.15±0.28;DEDAAC与AM和AA等共聚为非理想共聚,得到的产物均为无规共聚物.     

CrOx/ SBA-15介孔催化剂上丙烷在二氧化碳气氛中脱氢反应的研究

The structure and catalytic properties based on Chromium Oxide supported on mesoporous SBA-15 for oxidative dehydrogenation of propane by CO₂ have been studied by using X-ray diffraction (XRD), ultraviolet-visible diffuse reflectance spectra (UV-Vis DRS), electron spin resonance (ESR), X-ray photoelectron spectroscopy (XPS) and propane pulsing experiments in the absence of gas-phase O₂. It has been shown that propane conversion and propene yield increase with Cr loadings. The propane conversion and propene yield on CrO_x(Cr: 10wt%)/SBA-15 catalyst for oxidative dehydrogenation of propane by CO₂ at 550 ℃ reach 24.8% and 21.8%, respectively .The results of ESR, UV-Vis DRS and propane pulsing experiments indicate that Cr^Ⅲ in the CrO_x/ SBA-15 catalyst is the main active species in oxidative dehydrogenation of propane by CO₂ and Cr^Ⅵ, Cr^Ⅴ is inactive in dehydrogenation.     

~(13)C-NMR STUDY ON THE CHAIN TERMINAL STRUCTURE OF POLY-1,3-PENTADIENE POLYMERIZED WITH RARE EARTH CATALYST

The sequence distribution and the terminal structures of poly-1,3-pentadiene chains obtained by rare earth catalyst and effect of polymerization temperature on microstructure of the polymer have been investigated by ~(13)C-NMR method. According to experimental results it was supposed that terminal active growing chain of the polymer would be four types of anti- and syn-η~3-allyl structures. When polymerization temperature was reduced, the content of cis-1,4-poly-1,3-pcntadiene increases. It can be explained by isomerization between anti- and syn-η~3-allyl. The process forming trans-1,2 unit instead of 3,4-unit were also described.     

硝酸酯分子几何构型的量子化学研究

运用MINDO / 3、MNDO 和AM1 三种半经验分子轨道(MO)方法, 通过SCF计算, 首次系统地获得了32个硝酸酯化合物分子的全优化几何构型。三种方法的计算结果与已报道的四个化合物(硝酸甲酯、吉纳、硝化甘油和太安)的实验结果相比, AM1法较好。所有硝酸酯的酯基(-ONO~2)具有近似不变的几何参数。直链烷基硝酸酯的键长和键角极为相近, 全部重原子均共平面。二元直链和四元硝酸酯具有对称的分子构型。     

一种纳米TiO2粉体防团聚的新方法

开发了一种新的低成本防团聚方法——泡沫悬浮法。对泡沫悬浮法和共沸蒸馏法的防团聚效果进行了系统比较。结果表明，泡沫悬浮法可以有效抑制煅烧过程中纳米TiO₂晶粒的粗化和一次粒径的长大。泡沫悬浮法所得纳米TiO₂的粉体还具有团聚粒径小、粒度分布窄以及比表面积大的优点。通过FTIR、TG、DTA和松装密度实验对泡沫悬浮法的防团聚机理进行了研究，提出了纳米TiO₂防团聚模型。     

Reactivity Ratios of Diethyldiallylammonium Chloride with Acrylamide or Acrylic Acid

The compositions of copolymers of diethyldiallylammonium chloride (DEDAAC) with acrylamide (AM), acrylic acid (AA) or sodium acrylic acid (NaAA) at low conversion were determined by elemental analysis, and the reactivity ratios of monomers in copolymerization were obtained by Kelen-Tudos method. The results showed that the reactivity ratios rDE and rAM are 0.31 and 5.27 for DEDAAC with AM, rDE and rAA are 0.28 and 5.15 for DEDAAC with AA, and rDE and rNaAA are 0.40 and 3.97 for DEDAAC with NaAA, respectively. The copolymerizations for DEDAAC with AM, AA or NaAA are non-ideal copolymerization and the products are random copolymers.     

A,C-Bridged Calix[6]arene： Relationship between the Length of Bridge and Conformation

Three new A,C-diamide bridged p-tert-butylcalix[6]arenes were synthesized from p-tert-butylcalix[6]arenes by bridging ClCH2CONH(CH2)nNHCOCH2Cl(n=3,4,6) in acetonitrile using K2CO3 as a base in 17%-25% yields.It was found that the bridged calix[6]arenes with shorter bridges (n=2,3,4 in N′,N′-bischloroacetodiamines) adopt cone conformation, but the last one (n=6) adopts alternate conformation, i.e., accompanying the lengthening of bridge, the conformation of A,C-bridged calix[6]arenes changes from cone to alternate.     

室温无溶剂条件下醋酸锌催化的Knoevenagel缩合反应

以醋酸锌作为催化剂, 在室温无溶剂条件下催化芳香醛与活泼亚甲基化合物发生Knoevenagel缩合反应, 其反应条件温和, 产率最高可达100%, 产品纯度好, 操作和后处理简单.     

Effect of La2O3／γ—Al2O3 Catalyst on the Activation of CH4 and CO2 to C2 Hydrocarbons under Non—equilibrium Plasma

In the reaction of methane and carbon dioxide to C2 hydrocabons under non-equilibrium plasma, methane conversion was decreased,but selectivity of C2 hydroxarbons was increased when using La2O3/γ-Al2O3 as catalyst. So the yield of C2 hydrocarbons was higher than using plasma alone. The synergism of La2O3/γ-Al2O3 and plasma gave methane conversion of 24.9% and C2 yield of 18.1%. The distribution of C2 hydrocarbons changed when Pd-La2O3/γ-Al2O3 was used as catalyst,the major C2 product was ethylene.     

An Interesting Approach to Bis-calix[5]arene Analogue from Calix[6]arene

Calix [n] arenas {n = 4, 6 or 8} are easily prepared from formaldehyde and para-substituted phenols via cyclic condensation under alkaline conditions in one step. It is not surprising that the calyx [n] arene (n = 4, 6, 8) chemistry has been developing very rapidly during the latest 20 years1. However, it is not the case for calixarenes with odd benzene rings (for example, n = 5). The yield of p-tert-butylcalix [5] arene synthesized in one-step from p-tert-butylphenol and formaldehyde was a…