环境友好型离子液体催化环氧丙烷反应合成丙二醇醚

丙二醇醚类化合物是性能优良的精细化学品,也是环保型高级溶剂.该类化合物具有两个强溶解性功能基团—醚键和羟基,前者具有亲油性,可溶解疏水性物质,后者具有亲水性,可溶解亲水性物质,因而丙二醇醚具有很强的溶解能力,素有"万能溶剂"之称,可广泛应用于涂料、油墨、油漆、印刷、电子化学品、染料、净洗和纺织等行业.丙二醇醚类化合物目前主要由环氧丙烷和低级脂肪醇反应合成,然而,由于环氧丙烷的位阻效应,使其在酸或碱的条件下开环的位置会不同,从而得到不同的醇醚产物.由于碱催化的醇醚产物更加环境友好,因而越来越被人们所关注.工业上丙二醇醚合成多采用传统的强碱性催化剂醇钠以及氢氧化钠,腐蚀性强,产生的废液量大.本文采用环境友好的非卤素离子液体作为催化剂,研究了其催化环氧丙烷醚化合成丙二醇醚的反应特性.本文采用两步法合成了一系列环境友好的醋酸类碱性功能化离子液体,并在温和的条件下将其用于催化环氧丙烷与醇反应合成丙二醇醚.结果表明,该类离子液体可以高效催化该反应的进行.利用紫外-可见光谱测定Hammett指数来表征实验中所用离子液体的碱强度,并构建了离子液体碱性与催化活性之间的关系.结果表明,离子液体的催化性能和其碱性密切相关,随着离子液体碱性的增加,催化活性增强,其中咪唑醋酸类离子液体碱性强于季胺类,表现出优异的催化性能.离子液体的碱性明显弱于NaOH,但却呈现出更优异的催化性能.相同反应条件下,EmimOAc离子液体作为催化剂,PO的转化率分别较NaOH高出20%–30%,选择性略高于NaOH,这可能是由于二者催化机理不同造成的.传统NaOH催化机理的关键步骤是醇在碱性催化剂的作用下去质子化形成电子供体烷氧根离子,促进环氧丙烷的开环加成.而本文提出了离子液体亲电亲核双活化作用机理,即离子液体在阴阳离子之间的氢键和电荷相互作用的共同作用下,促进环氧丙烷开环和醇的去质子化,形成相应的反应中间体.通过电喷雾质谱分析手段检测到了阴阳离子通过协同作用亲电亲核催化过程中的反应中间体,证明了该假设机理的可行性.此外,还考察了催化剂浓度、醇比、反应温度以及醇的空间位阻效应对反应的影响.以EmimOAc催化合成丙二醇丁醚为例,反应的转化率随催化剂浓度的增加而增大,在催化剂添加量1%(催化剂与PO的摩尔比)时,PO转化率达到最大值为98.2%,1-丁氧基-2-丙醇的选择性为86.4%.当正丁醇与环氧丙烷的摩尔比为3时,转化率最高为88.6%,选择性高达94%.该反应为放热反应,最适反应温度约为140 oC,此时转化率高达96.5%.在环氧丙烷和不同的低碳醇合成丙二醇醚的反应中,反应物醇的碳链越短,支链越少,催化反应效率越高.     

NEW METHOD FOR LOW ORDER SPECTRAL MODEL AND ITS APPLICATION

In order to overcome the deficiency in classical method of low order spectral model, a new method for low order spectral model was advanced. Through calculating the multiple correlation coefficients between combinations of different functions and the recorded data under the least square criterion, the truncated functions which can mostly reflect the studied physical phenomenon were objectively distilled from these data. The new method overcomes the deficiency of artificially selecting the truncated functions in the classical low order spectral model. The new method being applied to study the inter-annual variation of summer atmospheric circulation over Northern Hemisphere, the truncated functions were obtained with the atmospheric circulation data of June 1994 and June 1998. The mechanisms for the two-summer atmospheric circulation variations over Northern Hemisphere were obtained with two-layer quasi-geostrophic baroclinic equation.     

液晶润滑添加剂的减摩作用机理研究

液晶润滑添加剂具有优良的减摩性能，但在已有的文献报道中涉及其减摩机理的研究内容却还很少。因此，利用向列型液晶材料已氧基苯甲酸和正辛基苯甲酸作为ＨＵ－２０汽轮机油的添加剂，在给定的压力、速度和温度条件下于Ｆａｌｅｘ试验机上进行了液晶的减摩性能试验研究，并且用Ｘ射线衍射、俄歇电子能谱和扫描电子显微镜等技术，对溶解于矿物油中的液晶结构、磨损表层的元素组成及其表面形貌作了观察、分析与研究，在此基础上又对液     

Vibration reduction in a flexible-link mechanism through synthesis of an optimal controller

In this paper, reduction of vibration of a flexible planar mechanism is achieved through synthesis of an optimal controller. A finite element model, based on the equivalent rigid-link system theory, is used to accurately describe the dynamic behavior of the system. The model, which accounts for geometric and inertial nonlinearities of the mechanism, has been fully validated through experimental tests. In order to be able to employ the classical optimal control theory, a suitable linear model has been derived from the original one by means of a suitable linearization procedure. Vibration reduction can then be obtained by first defining an adequate performance index, which accounts for vibration amplitude, then by solving Riccati’s equation in order to find the controller that minimizes the performance index, i.e. the optimal controller. The results of several tests that have been carried out are also reported, to show the effectiveness of the synthesized control system.     

损伤和断裂的统一

本文讨论了连续损伤力学基础的缺陷,从微裂纹随机演化出发给损伤概念作出新的普适的统计定义,导出了损伤断裂几率的动力学方程,使损伤、断裂、统计、微观机理及宏观特性五者有机地相结合,从而有可能形成一个统一的损伤断裂微观统计理论。     

山东龙口北皂煤矿软岩力学特性实验研究

根据室内实验结果, 本文讨论了北皂煤矿的岩石力学性质, 物化特性。泥质岩类的力学性质和水理性质、物化特性有关。泥质岩类具有显著的流动变形和各向异性。     

杆和梁在锁定过程的响应

对杆和梁在锁定过程的响应进行了详细分析，用波传播理论解释了部分结果的物理含义，对用Ｅｕｌｅｒ梁理论分析锁定问题的可行性进行了探讨。     

Tris(4-anisyl)phosphine as an Efficient and Practical Reagent for the Synthesis of (E)-2-Benzylidenesuccinates

Condensation of maleic anhydride or dimethyl maleate with benzylaldehydes controlled by tris(4‐anisyl)‐phosphine to synthesize dimethyl (E)‐2‐benzylidenesuccinates has been systematically investigated. The protocol gives the product with high stereoselectivity in moderate to good yields under mild conditions. A plausible mechanism has been proposed.     

TiO_2纳米管阵列薄膜制备及生长机理的研究

本论文采用阳极氧化的方法,在NH4HF2+NH4H2PO4的混合水溶液中于室温下以金属钛为基体原位合成氧化钛纳米管阵列薄膜。讨论了电解液成分、外加电压、溶液的pH值对氧化钛纳米管阵列薄膜微观结构及形貌的影响,并建立了阳极氧化钛纳米管阵列薄膜的生长模型。氧化钛纳米管的结构与外加电压有很大的关系,只有电压在5～35V范围内才能制备出二氧化钛纳米管阵列薄膜,其管径随着电压的升高而增加,且管径范围为30～160nm。而薄膜的厚度与电解液有关,通过控制电解液的成分及pH值,可获得厚度为6.5μm的氧化钛纳米管阵列薄膜。     

Non-isothermal Decomposition Mechanism and Kinetics of LiClO4 in Nitrogen

The non-isothermal decomposition kinetics of LiClO4 in flow N2 atmosphere was studied.TG-DTA curves show that the decomposition proceeded through two well-defined steps below 900°C,and the mass loss was in agreement with the theoretica1 value.XRD profile demonstrates that the product of the thermal decomposition at 500°C is LiCl.For the decomposition kinetics study,the activation energies calculated with the Friedman method were considered as the initial values for non-linear regression and were used for verifying the correctness of the fitted models.The decomposition process was fitted by a two-step consecutive reaction:extended Prout-Tompkins equation[Bna,f (α) is (1?α)nα a] followed by a 1th order reaction(F1).The activation energies were (215.6±0.2) and (251.6±3.6) kJ/mol,respectively.The exponentials n and a for Bna reaction were (0.25±0.05) and (0.795±0.005),respectively.The reaction types and activation energies were in agreement with those obtained from the isothermal method,but the exponentials were optimized for better fitting and prediction.