乙酸乙酯制备反应的理论研究——计算化学在基础有机化学实验中的应用(I)

对乙酸乙酯制备的酯化反应进行密度泛函理论的B3LYP和微扰理论的MP2计算,得出反应的热力学参数,并从热力学的角度考查了酯化反应的特点.     

张峰水库输水工程总干后半段方案比选

通过对原输水工程初步设计方案的分析,对多个方案进行了比选,并确定了输水方案。     

具Ⅱ型Hlling功能性反应捕食系统解的性质

研究一个齐次Neumann边界条件弱耦合的反应扩散系统.利用Lyapunov函数及局部稳定性给出了正常数解全局渐近稳定的充分条件,并由此说明,只要食饵的出生率足够大、或者捕食者的捕获率足够小、或者捕食者的内部竞争充分强,正常数解就是全局渐近稳定的.另外,还证明了只要一个物种的扩散率足够大,则稳态系统不存在非常数解.     

生质柴油碱性均匀相触媒制程研究

生质柴油为重要之可再生能源。本文研究改善液相触媒制程,以降低甲醇与三酸甘油酯间界面阻力,以提生反应速率。实验结果发现,在批式制程中,提高搅拌速率可提升反应速率,然因工厂实际操作恐有困难。以相转移触媒可达增加反应速率与产率效果,但需注意选用之相转移触媒不可在强碱下被破坏。使用共溶剂THF可促进反应速率与产率,为一可行的选择。而连续制程较批式制程有较好的效率。     

一类带有局部化源的反应扩散方程组解的整体存在性及爆破

考虑一类带有局部化源项的反应扩散方程组.在适当的假设下,用上、下解法得到了该问题的解在有限时刻爆破及整体存在的充分条件.     

Bis-Wittig反应法合成不对称二烯腊肪酸酯

双季鏻盐1与n-BuLi反应生成膦双叶德2,接着与两种不同的醛发生bis-Wittig反应成功地合成了天然产物二烯脂肪酸甲酯7a及两个新的类似物7b和7c,产率为24%～30%.该法具有原料易得,路线短等特点.产物的结构用IR、1HNMR、和Ms等进行了表征.图3,参16.     

热超声倒装键合机视觉系统的设计与实现

针对热超声倒装键合过程中对准工作的特点,确定合理的视觉自动对准方案,在对多种颜色和形状的LED光源进行实验对比的基础上,设计环形LED光源与单个LED发光二极管组合的照明方式,使芯片、基板表面亮度一致且表面几何特征清晰。视觉软件以HexSight为核心,利用创建参考点实现不同目标的识别,并对2个CCD摄像机的控制方案进行优化。通过分析多次识别结果对单项误差进行评估,并以实验用1 mm×1 mm的表面有8个凸点的芯片为例计算视觉识别系统的综合误差,结果表明此视觉识别系统满足芯片键合时对定位精度的要求。     

标准态下碳酸二甲酯合成体系热力学分析

 用Benson基团贡献法计算了碳酸二甲酯(DMC)的热力学数据标准摩尔生成焓Δ_fH_m^θ、标准摩尔生成吉布斯自由能Δ_fH_m^θ和等压摩尔热容C_p,m;在标准态下,300~1 000 K温度范围内对比了甲醇或二甲醚(DME)氧化羰化合成DMC,甲醇或DME与CO₂直接合成DMC,由合成气合成DMC,DME,甲醛或甲醇这些反应的焓变Δ_fH_m^θ、吉布斯自由能变Δ_fH_m^θ和平衡常数lnK^θ.计算结果表明:在讨论的条件范围内,由DME氧化羰化合成DMC是热力学上可自发进行的反应,但DME和CO₂反应合成DMC与甲醇和CO₂反应合成DMC,均不能自发进行(需要通过耦合等方式来改变反应途径或重构反应体系,该反应才有可能进行).此计算将为合成DMC的反应路线设计以及新催化剂体系的探索提供热力学依据.     

Preparation of polypropylene/montmorillonite nanocomposites by intercalative polymerization： Effect of in situ polymer matrix functionalization on the stability of the nanocomposite structure

The copolymerization of propylene and 5-hexenyl-9-borabicyclo[3.3.1]nonane (5-hexenyl-9-BBN) has been conducted with an MgCl2/TiCl4 catalyst intercalated in an organically modified montmorillonite (OMMT) with triethylaluminum (AlEt3) cocatalyst and diphenyldimethoxysilane (DDS) external donor. This polymerization process simultaneously results in both the exfoliation of MMT layers to realize the preparation of polypropylene (PP)/MMT nanocomposites and the implantation of reactive borane groups in the formed PP matrix. The polymer-borne borane groups have been able to undergo an effi-cient hydrolysis process under very mild reaction conditions (40℃, 3 h, in THF), introducing hydroxy groups into PP without sacrificing the polymerization-formed nanocomposite structure (the exfoliation of MMT). The resultant hydroxyl-functionalized PP/MMT nanocomposites exhibit enhanced structural stability against processing compared with those based on unfunctionalized PP matrix.     

Experimental investigation of incremental reactivity of di-tert-butyl peroxide

Large quantities of di-tert-butyl peroxide (DTBP) have been emitted into the troposphere due to human activities. Its role in the atmospheric photochemical reaction has not been understood. This study presents the results of the photochemical reactions of DTBP and NOx, which have been simulated in a self-made smog chamber under the temperature of (29±1)℃. Both the wall decays of ozone and NO2 could be neglected, compared to the results in simulative experiments. The effective intensity of UV light used in the experiments was 1.28×10-3 s-1, which was expressed by the rate constant of NO2 photolysis in purified air. The reaction mechanism was proposed according to our results and reports of other researchers. The maximum values of incremental reactivity (IR) in the three simulative ex- periments were 9.53×10-2, 5.23×10-2 and 3.78×10-2, respectively. The incremental reactivity decreased with the increase of initial concentrations of DTBP. The IR value of DTBP obtained in this study was comparable to that of acetylene reported in our previous research.