基团转移聚合单体引发活性研究

<正> 基团转移聚合(GTP)是Webster等发现的一种合成高分子的新手段,能在相当温和的条件下进行,能成功地控制聚合过程及产物的微观结构,从而达到控制产品性能的目的。因此在高分子设计方面具有重要的地位。 适用于GTP的单体目前主要有三类:丙烯腈,丙烯酸酯及甲基丙烯酸酯类化合物。本文使用三种活性不同的引发剂:1-甲氧基-1-三甲基硅氧基-2-甲基丙烯[Me_2C=     

GIS支持下降雨滑坡的启动机制研究与数字仿真

大气降雨对滑坡体的含水量和容重均有影响, 该影响具有一定的时间进程, 同时滑坡滑带土的含水率对内摩擦角和内聚力均有一定的影响。本文提出了滑坡启动的两种不同机制。通过降水滑体含水率滑体容重、滑带土内摩擦角、内聚力以及它们与滑坡稳定系数的定量关系及其时间效应, 建立起滑坡启动的速度、推力、方向和启动时间的预测、预报模型。     

Detecting cavitation in globe valves by two methods: Characteristic diagrams and acoustic analysis

Cavitation is a dynamic phenomenon that occurs in fluid flows when the local pressure is lower than the saturated vapor pressure at ambient temperature. The formation and collapse of cavitation bubbles leads to corrosion and pitting of metal surfaces. Considering the fact that damage to moving parts caused by cavitation has serious consequences it is important to be able to detect it. In this research an attempt is made to study the development of cavitation in globe valves using two different methods: characteristic diagrams and acoustic measurement. The results of the two methods are found to be in general agreement within acceptable levels of accuracy.     

Analysis of critical dynamics for shock-induced adiabatic explosions by means of the Cauchy problem for the shock transformation

We present a theoretical and numerical study on the induction of adiabatic explosions by accelerated curved shocks in homogeneous explosives, and pay a special attention to critical conditions for initiation. We characterize the first stage of the decomposition process, or induction, as an initial-value problem. During induction, the reaction progress-variable remains small; the induction time is given by the runaway of the dependent variables and corresponds to a logarithmic singularity in theirs material distributions. We express these distributions as first-order expansions in the progress variable about the shock. Then, the framework of our procedure is the formal Cauchy problem for quasi-linear hyperbolic sets of first-order differential equations, such as the balance laws for adiabatic flows of inviscid fluids considered in this study. When a shock front is used as data surface, the solution to the Cauchy problem yields the flow derivatives at the shock, then the induction time, as functions of the shock normal velocity and acceleration, and , and the shock total curvature C. We next derive a necessary condition for explosion as a constraint among , and C that ensures bounded values of the induction time. This criterion is akin to Semenov's, in the sense that the critical condition for explosion is that the heat-production rate must just exceed the heat-loss rate, here given by the volumetric expansion rate at the shock. The violation of the criterion defines a critical shock dynamics as a relationship among , and C that generates infinite induction times. Depending on the rear-boundary conditions, which determine the shock dynamics, this event can be interpreted as either a non-initiation, or the decoupling of the shock and of the flame front induced by the shock. We illustrate our approach by a simple solution to the problem of the initiation by impact of a noncompressible piston. From the continuity constraint in the material speed and acceleration at the contact surface of the piston and the explosive, we first derive the initial shock dynamics, and then rewrite the induction time and the initiation condition in terms of the piston speed, acceleration and curvature. We compare these theoretical predictions to those of our direct numerical simulations, and to numerical results obtained by other authors, in the case of impacts on a gaseous explosive. Received 19 October 1998 / Accepted 1 June 1999     

DCC/AlCl_3体系引发异丁烯正离子聚合

研究以对-二枯基氯(DCC)/AlCl3体系引发异丁烯在CH2Cl2/Hex(40/60,V/V)混合溶剂中进行正离子聚合,探讨了DCC用量、给电子试剂,如三苯胺(TPA)、2,6-二甲基吡啶(DMPy)对异丁烯正离子聚合转化率、产物分子量及其分布的影响.结果表明,在无给电子试剂存在时,DCC和体系中微量水均可与AlCl3产生络合竞争引起相继的引发竞争,聚合产物GPC谱图呈双峰分布,分子量分布宽,需要大量的引发剂DCC(DCC/H2O=5.3)来减少体系中微量水的不可控引发;在少量上述给电子试剂存在下,可提高DCC的引发效率,减少向单体链转移反应,提高聚合产物的分子量和使分子量分布呈较窄的单峰分布,即使在较低DCC用量下也可基本抑制体系中微量水的不可控引发,达到DCC定量引发,并得到分子量分布相对较窄(Mw/Mn≈2.3)的聚异丁烯产物.     

Bond-Forming Initiation in Spontaneous Addition and Polymerization Reactions of Alkenes

Spontaneous addition and polymerization reactions of alkenes of different electron-densities result in a wide variety of small organic molecules and high polymers. Tetramethylenes are proposed as key intermediates, i.e. resonance hybrids of 1,4-diradical and zwitterionic limiting structures. Their character is determined by the substituents at the terminals: Zwitterionic character is favored by strong donors, such as alkoxy and dialkylamino groups, at the carbenium center and strong acceptor group such as diesters and cyano-esters, at the acceptor end, and aryl and vinyl groups as donors. Zwitterionic tetramethylenes initiate ionic homopolymerization, while diradical tetramethylenes initiate alternating copolymerization, thus providing an extremely sensitive technique for the detection and characterization of these intermediates. The effects of the donor and acceptor substituents can be arranged as an “Organic Chemist's Periodic Table”, wherein the areas of mechanistic change clearly emerge and which provides predictive capability.—This unifying concept of bondforming initiation is extended to spontaneous addition and polymerization reactions of heteroatom acceptor molecules and 7,7,8,8-tetrasubstituted quinodimethanes and of compounds possessing labile σ-bonds, such as halogens and peroxides. Radical-ion pairs, charge-transfer complexes and adventitious impurities are excluded as significant initiators.     

过硫酸盐和脂肪环胺体系引发机理的ESR研究

用ESR方法研究了过硫酸盐和脂肪环胺吗啉,哌啶及其N-烷基取代衍生物体系引发反应的初级自由基,结合端基分析,证实了这类脂肪环胺与过硫酸盐反应产生的初级自由基都能引发烯类单体聚合。当所用的是脂环仲胺时,其初级自由基为氮中心自由基;用脂环叔胺时,初级自由基是N-烷基的α-碳中心自由基。     

高速远程地震黄土滑坡发生机制试验研究

研究了一种新的远程导弹飞行轨道的可行性,它的最大飞行高度约100km. 这种 超低弹道,借鉴卫星模式,利用离心力抵抗重力. 与卫星轨道运行不同的是,超低弹道周围 的稀薄空气影响至关重要,必须考虑. 计算和分析结果表明,在相同载荷条件和射程条件下, 超低弹道和经典的最小能量弹道对于火箭动力的需求大致相当,射程10000km以上基本相同. 头部半径为5cm的轴对称外形,沿超低弹道飞行时,其驻点热流在高度26km左 右达到最大值 50MW/m2, 约为最小能量弹道驻点热流最大值的50%. 由于超低弹道对升力没有要求, 飞行过程中的气动加热问题,沿用成熟方法如烧蚀防热即可解决. 总体而言,超低弹道对于 火箭动力与外形气动力/热要求,现有技术容易满足,因此利用它增强远程导弹的突防能力是 现实可能的.     

HES/TiCl4体系引发异丁烯可控正离子聚合

由六官能团引发剂环氧化角鲨烯(HES)与TiCl4组成引发体系,引发异丁烯(IB)在CH2Cl2/n-Hex(40/60,V/V)混合溶剂中进行正离子聚合,分别探讨了HES和2,6-二甲基吡啶(DMP)用量对IB正离子聚合转化率、产物分子量及其分布的影响.结果表明HES和微量水均可与TiCl4发生络合,并分别形成碳正离子和质子两种引发活性中心,导致聚合产物GPC谱图呈明显双峰分布.增加引发剂HES用量([HES]=2.64mmol/L),可以减少聚合体系中微量水的不可控引发,提高HES引发效率;在聚合体系中引入少量DMP时,可明显地减少微量水的不可控引发和提高HES的引发效率,使得即使在较低HES用量下([HES]=0.084mmol/L),也可达到主要由HES引发IB正离子聚合,制备出官能叔氯末端的六臂星形支化遥爪聚异丁烯,GPC谱图呈现单峰分子量分布,分布指数为1.5左右.