原子转移自由基聚合的动力学模型化研究

原子转移自由基聚合(ATRP)是“活性”/可控自由基聚合方法中研究最为广泛的一种,它不仅适用单体广泛、反应条件温和,而且可以方便地对聚合物进行结构设计.为了能够更深入地了解和控制聚合过程,通过ATRP动力学模型化并耦合不同操作方式下的反应器模型已成为必然,它可以更精确地控制大分子链结构,如分子量及其分布、共聚组成及组成分布,同时还能优化聚合条件.从传统自由基聚合理论入手并结合ATRP与传统 自由基聚合的异同,本文首先论述了ATRP动力学模型化过程;其次系统综述了已有的ATRP动力学模型研究,着重对三类不同的数学模型处理方法(矩方法,蒙特卡罗法、商业软件包-PREDICI,GEPASI等)进行了总结.     

无机膜反应器中丙烷脱氢制丙烯的数学模型

建立了模拟实验室膜反应器的两种数学模型，活塞流模型和多级全混流模型，将实验数据应用于所建模型，在不同的空速，临氢比、吹扫气流速、温度和膜位置等条件下，拟合出丙烷脱氢的表观活化能、指前因子和表观反应级数，计算结果与实验结果相当符合。     

受限空间下的烯烃聚合研究

近些年来,随着纳米技术的发展,出现了很多微纳米反应器,该反应器能够提供具有纳米尺寸的反应环境,使得在该环境下进行的反应受到纳米空间的影响,生成具有纳米效应或特殊结构的产物。在聚烯烃催化聚合中,也出现很多具有受限空间的微纳米反应器载体,这些载体不仅能够负载烯烃催化剂,还能为烯烃聚合反应提供受限空间环境。在纳米尺度效应的影响下,催化烯烃聚合进程发生变化,可以得到一些具有特殊结构与性能(比如高熔点、超高分子量、纤维状)的聚烯烃产物。本文总结现阶段受限空间下烯烃聚合研究的最新成果,主要根据聚合物的不同结构进行分类,分别介绍了受限空间对聚烯烃产物的形貌、反应动力学及活性、初级结构、二级结构和凝聚态结构及性能的影响,并对受限聚合研究的发展趋势进行了展望。     

丙烯腈尾气协同脱除多段组合催化动力学研究及CFD模拟

本文通过筛选出几种适用于不同气体脱除的最佳催化剂及明确催化剂最优组合顺序,采用固定床微型反应器进行丙烯腈尾气催化燃烧试验考察,获得本征动力学数据,并对动力学数据的可靠性进行计算验证;采用CFD数值模拟软件建立多孔介质二维数学模型,在实际工业废气条件下,对废气组分催化燃烧反应进行模拟,分析操作参数对废气催化燃烧特性的影响.通过模拟获得丙烯腈尾气脱除的最佳操作条件(流速:30000 h~(-1),入口温度:623 K,组分摩尔比:10:1,催化剂床层孔隙率:～0.7);在该最佳操作条件下,对两段式催化反应器进行模拟,得到了压降和绝热温升等反应器参数.     

用局部组成模型对NaCl-Na2SO4-H2O体系变温下的相平衡的计算和预测

采用局部组成模型理论,建立了不同温度下Na //CI-,SO42- -H2O体系的热力学模型.利用该模型对此体系在不同温度下的溶解度进行了预测,并与实验数据对比,研究了模型对于此体系多温情况的适用性.由局部组成理论中的两离子相互作用能量参数以及不同温度下体系溶解度实验数据,通过Mattab优化函数,获得不同温度下各盐的活度积和两离子混合作用参数,并利用 Matlab非线性方程求解函数,预测了体系在0～150.C范围内的液固平衡数据,与实验数据及Pizter模型汁算结果进行对比.研究结果表明.局部组成模型的多温适用性良好,预测结果与实验数据基本一致.     

升温与等温法非模型动力学研究环氧树脂固化反应

基于DSC数据,采用以Vyazovkin积分法为基础的升温法非模型动力学和等温法非模型动力学对双酚A型环氧树脂E51/4,4′-二氨基二苯基砜(DDS)体系及多官能度环氧树脂AG80/DDS体系的固化过程进行了研究,并结合玻璃化转变温度的变化和原位红外测试技术,对比分析了升温与等温条件下的固化反应规律.结果表明,与传统的模型拟合法相比,非模型动力学更适合定量预测树脂固化反应过程,并能为固化过程中反应机理变化的研究提供重要依据;等温法非模型动力学能够更好地预测两种树脂体系在不同恒温条件下的固化反应历程,并且升温法与等温法非模型动力学所得到的反应活化能-固化度之间的变化关系不同,表明不同温度条件下树脂的反应机理不同,这与升温和恒温条件下玻璃化效应及环氧官能团的变化规律相吻合.     

高温高压的流动溶液内矿物-水反应动力学研究

本文着重介绍高温高压下开放流动体系内矿物-水反应动力学的最新研究成果。在研究了连续流动体系中方解石-水的反应速度方程后又在稳态操作的化学动力学实验中发现了偶存于其中的非稳态动力学过程。同时用轴向弥散模型和叠层反应器研究了萤石和钠长石反应动力学机理。本文还研究了不同温压、流速、介质和不同的溶液性质对反应速度的影响及控制因素。     

70～580 K小样品全自动精密绝热量热装置的建立--α-Al2O3的摩尔热容

建立了样品池容积为 7.4cm3 ,可在 70～ 5 80K温区工作的小样品量自动绝热量热计 .量热计设置有两层绝热屏 ,三层辐射屏及辅助控温套 ,以保证高温下量热系统良好的绝热条件 .样品池主体用紫铜制作 ,带有装卸管的容器上盖用黄铜制作 ,紫铜压帽盖与装卸管用螺纹连接铅锡合金垫片密封 ,保证样品池在整个实验温区保持高真空密封不泄漏 .量热计所有导线采用W30 11有机硅耐高温漆绝缘和固定 ,使量热计电测系统在高温下具有良好的稳定性 .所有量热测试数据 ,包括电能和温度的测量 ,全部由计算机按预定程序自动采集和处理 .测量量热标准物质α Al2 O3 的摩尔热容 ,检验了所建量热装置的可靠性 .α Al2 O3 的摩尔热容实验值与舒平值的标准偏差为± 0 .2 8%,与美国标准局数据比较 ,相对偏差在± 0 .4%以内     

环氧乙烷环氧丙烷共聚醚的研究进展

综述了环氧乙烷环氧丙烷共聚醚的聚合机理聚合工艺及其应用.环氧乙烷环氧丙烷共聚醚的聚合按其催化剂体系的机理可以分为阴离子聚合、阳离子聚合和配位聚合三类,其中阳离子聚合应用较少.在环氧乙烷和环氧丙烷开环聚合生成共聚醚的反应中,不同的反应工艺条件对生成的聚醚有着很大的影响.同样比例的环氧乙烷和环氧丙烷,因聚合反应器设计、反应器种类、起使剂种类催化剂种类与用量温度加料方式端基结构等的不同,所合成的共聚醚会产生不同的结构和性能.环氧乙烷环氧丙烷共聚形成的聚醚可以分为嵌段共聚醚和无规共聚醚两类.其中,嵌段共聚醚可以分为EPE和PEP两类.     

间歇反应器内醋酸丁酯酯化反应与渗透汽化集成过程的模型计算

 建立了一个间歇反应器内酯化反应与渗透汽化集成过程的数学模型, 用于描述反应和脱水同时进行的过程. 该模型考虑了反应体系中所有组分的渗透量影响以及混合物的非理想热力学行为. 选择乙酸和正丁醇生成醋酸丁酯的酯化反应与 PVA 膜渗透汽化集成过程为研究体系, 将模型结果与文献中已报道的实验数据进行对比, 验证了该模型的有效性. 结果表明, 采用渗透汽化脱除酯化反应的水分将提高酯的产率. 对温度、反应物初始比、膜面积与反应体积比以及催化剂浓度几种操作条件对集成过程性能影响进行了参数的分析. 根据结果讨论得到该膜过程与反应集成过程的优化操作条件.     

Frontal polymerization synthesis of starch-grafted hydrogels: Effect of temperature and tube size on propagating front and properties of hydrogels

The frontal polymerization process was used to produce superabsorbent hydrogels based on acrylic acid monomers grafted onto starch. Using a simple test tube which was nonadiabatic and permitted contact with air, the effects of initial temperature and tube size on the propagating front of grafting copolymerization and the properties of hydrogels were explored. The unrestricted access of the reaction mixture to oxygen delayed the formation of self-propagating polymerization front. The ignition time was markedly lengthened with the increasing of tube size attributed to the formation of large amounts of peroxy radicals. The front velocity dependence on initial temperature could be fit to an Arrhenius function with the average apparent activation energy of 24 kJ mol(-1), and on tube size to a function of higher order. The increase of the initial temperature increased the front temperature, which lead to more soluble oligomers and higher degree of crosslinking. The interplay of two opposite effects of oligomer and crosslinking determined the sol and gel content. An increase in tube size had two effects on the propagating front. One was to reduce heat loss. The other effect was to increase the number of escaping gas bubbles. The combined action of the two effects resulted in a maximum value of front temperature, an increase in sol content and a reduction in gel content with tube size. The highest swelling capacity of hydrogels was obtained when the initial temperature or tube size favored a formation of porous microstructure of hydrogels.     

Reaction of silicon tetrafluoride with calcium hydride as a propagating wave

The synthesis of silane by reacting silicon tetrafluoride and calcium hydride is shown to proceed as a propagating wave. The main parameters of the process, namely, the propagation velocity, the reaction front temperature, and calcium conversion, are determined. The mathematical model of wave propagation for an exothermic reaction in a porous medium with purging a gaseous oxidant describes qualitatively the major laws of the process.     

Molecular dynamics study of the response of nanostructured Al/Ni clad particles system under thermal loading

Molecular dynamics simulations are used to study the exothermic alloying reactions by imposing a thermal loading on a local area of nanostructured Al/Ni clad particles. The combustion parameters, such as particles size, density, and ignition temperature, are characterized. Reducing the size of Al/Ni clad particles makes the propagation velocity of reaction front increase but lowers both the adiabatic combustion temperature and pressure of the system. However, increasing either mass density or ignition temperature makes the propagation velocity of reaction front increase and raises the adiabatic temperature and pressure as well. We estimate the propagation velocity of the chemical reaction front to range from 35.70 to 44.06 m/s.     

Oscillatory and stationary convective patterns in a reaction driven gravity current

Horizontally propagating chemical fronts are studied in a thin solution layer of the acid-catalyzed chlorite-tetrathionate reaction. Unusual cellular patterns develop when significant amount of autocatalyst is bound to polyelectrolyte with low mobility: both oscillatory and stationary patterns evolve as a result of the interaction between the reaction front and the superposed gravity current. The concentration of the polyelectrolyte regulating the velocity of front propagation serves as a bifurcation parameter for switching between the two basic patterns.     

前端聚合制备多孔聚丙烯酰胺水凝胶——溶剂和引发剂对反应和产物的影响

利用前端聚合结合发泡工艺制备了孔结构可调控的聚丙烯酰胺多孔水凝胶.研究发现溶剂和引发剂浓度变化对聚合前端的移动及形成的产物性能有重要影响.增加溶剂用量,聚合前端的移动速度和聚合前端最高温度下降,产物孔径增大,孔壁变厚,材料吸水溶胀性能降低;增加引发剂浓度,聚合前端移动速度显著加快,最高温度升高,产物的孔体积和溶胀率先增加后减小.     

Factors affecting propagating fronts of addition polymerization: Velocity,front curvature,temperatue profile,conversion, and molecular weight distribution

Several properties of propagating fronts of addition polymerization were studied. A power function could be fit to the velocity dependence on initiator concentration, but not with the exponents predicted by current models or in agreement with other published work. Bubbles from the volatile by-products of initiator decomposition were found to affect the front velocity and curvature. The front velocity for triethylene glycol dimethacrylate polymerization was found to depend linearly on temperature over a moderate range. The conversion of methacrylic acid in fronts varied greatly with initiator type and concentration. Benzoyl peroxide produced much lower conversion than t-butyl peroxide, but fronts with tBPO propagated slower. A dual initiator system of BPO and tBPO produced rapidly propagating fronts with good conversion but the contribution of each initiator to the velocity was not additive. The possibility of chain branching was considered. The apparent molecular weight distributions were very broad, often trimodal, and found to depend on initiator type and concentration as well as the tube diameter. The temperature profiles were measured and found to be very sharp for BPO and broader for tBPO but both had front temperatures in excess of 200°C, indicating a high ceiling temperature. © 1995 John Wiley & Sons, Inc.     

Discontinuously propagating waves in the bathoferroin-catalyzed Belousov-Zhabotinsky reaction incorporated into a microemulsion

Three new types of discontinuously propagating waves are reported in the bathoferroin-catalyzed Belousov-Zhabotinsky (BZ) reaction dispersed in water-in-oil Aerosol OT microemulsion. Jumping waves (JWs) are typically observed at or above room temperature and develop from the familiar trigger waves. Bubble waves (BWs) typically emerge from trigger or JWs at similar temperatures, while rotating waves (RWs) evolve from JW at higher temperatures (>40 degrees C). All these waves propagate discontinuously in a saltatory fashion. Other characteristic features include a discontinuous front for BW consisting of small concentric waves (bubbles) and lateral rotation of annular RWs. All three types of waves, as well as segmented but continuously propagating waves, can coexist. A simple model that is able to describe both jumping and segmented waves is described.     

加压流化床流化性质的实验与模拟研究

在二维射流流化床装置中,考察了压力对颗粒和气泡运动的影响规律.通过使用摄像技术详细的记录了压力下气泡的行为,并对其进行了分析,由此解决了较高压力下测量流态化性质较为困难的问题.数值研究通过CFD双欧拉模型模拟了带有V形分布器和中心射流的二维流化床内压力对气泡大小、床的膨胀率和射流深度的影响.实验和理论结果表明,在加压状态下,射流气速和分布板气速对气泡的产生、大小及形状有不同的影响.在较高的操作压力下,射流气速增加,气泡变长;分布器气速增大,气泡则变大;射流高度随着分布器气速的增加而降低.模拟结果与实验数据吻合较好,由此该模型为研究较高操作压力下射流流化床流化性质提供了有利的工具.     

Effect of orientation on thermoset frontal polymerization

We observed that the velocities of descending thermoset polymerization fronts were strongly affected by the orientation of the tube. The front remained approximately perpendicular to the gravitational vector but propagated almost 1.8 times as fast at 75° along the axis of the tube. We performed a study of the velocity and front‐shape dependence on orientation with propagating fronts of triethylene glycol dimethacrylate with peroxide initiator and acrylamide/bisacrylamide polymerization in dimethyl sulfoxide with persulfate initiator. The percentage increase of velocity was independent of the initiator concentration but strongly dependent on the viscosity. Convection under the front flowed away from the tube wall nearest the vertical axis and was stronger as the angle increased. The front shape also changed, becoming significantly distorted near the wall from which the convection originated. We applied a simple geometric argument to explain the angular dependence for small angles on the basis of the assumption that convection did not affect the velocity of propagation normal to the front. The increase in velocity along the tube axis could be explained by a projection of the normal velocity onto the tube axis, following a 1/cosθ dependence. For higher angles, the convection was not sufficiently strong to maintain a level front. When the difference from a 180° orientation was considered, the velocity dependence exactly followed the geometric relationship. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3504–3508, 2002     

Sensitivity of an exothermic chemical wave front to a departure from local equilibrium

We study the propagation of an exothermic chemical wave front in a reactive dilute gas and show that the particle velocity distribution departs from the Maxwellian form in the front zone. The analytical corrections to the balance equations for concentrations, temperature, and stream velocity induced by the departure from local equilibrium are derived from a perturbative solution of the Boltzmann equation. Our analytical predictions of the front properties, including its propagation speed, compare well with microscopic simulations of the particle dynamics.